Non-toxic corrosion-protection pigments based on manganese
Corrosion-inhibiting pigments based on manganese are described that contain a trivalent or tetravalent manganese/valence stabilizer complex. An inorganic or organic material is used to stabilize the trivalent or tetravalent manganese ion to form a compound that is sparingly soluble, exhibits low solubility, or is insoluble in water, depending upon the intended usage. Specific stabilizers are chosen to control the release rate of trivalent or tetravalent manganese during exposure to water and to tailor the compatibility of the powder when used as a pigment in a chosen binder system. Stabilizers may also modify the processing and handling characteristics of the formed powders. Manganese/valence stabilizer combinations are chosen based on the well-founded principles of manganese coordination chemistry. Many manganese-valence stabilizer combinations are presented that can equal the performance of conventional hexavalent chromium or tetravalent lead systems. It is emphasized that this abstract is provided to comply with the rules requiring an abstract which will allow a searcher or other reader to quickly ascertain the subject matter of the technical disclosure. It is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims.
[0001] This application is related to commonly assigned U.S. patent application Ser. No. ______, (Attorney Docket No. UVD 0318 PA) NON-TOXIC CORROSION—PROTECTION PIGMENTS BASED ON PERMANGANATE AND MANGANATE, filed Jan. 13, 2003 by Sturgill et al., the disclosure of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION[0002] This invention relates generally to compositions and methods for the formation of protective, corrosion-inhibiting pigments without the use of chromium in the hexavalent oxidation state or lead in the tetravalent oxidation state. More particularly, this invention relates to non-toxic, corrosion-inhibiting pigments based on trivalent and tetravalent manganese and methods of making and using the same.
[0003] Inhibiting the initiation, growth, and extent of corrosion is a significant part of component and systems design for the successful long-term use of metal objects. Uniform physical performance and safety margins of a part, a component, or an entire system can be compromised by corrosion. Aluminum, zinc, iron, magnesium, titanium and their alloys tend to corrode rapidly in the presence of water due to their low oxidation-reduction (redox) potentials. The high strength 2000 and 7000 series of aluminum alloys are used extensively in aircraft and are very sensitive to corrosive attack. Materials such as steels and carbon fibers with higher redox potentials will form a galvanic couple in water and promote corrosive attack when located near light metal alloys such as aluminum.
[0004] A bare metal surface or one that has been conversion coated, phosphated, sealed, rinsed, or otherwise treated will be protected by the application of a primer paint with a corrosion inhibiting pigment. As used herein, the term “pigment” means chemically active compounds with the ability to inhibit corrosion at a distance, rather than simple colorants or opacifiers. Oxidative compounds that are effective as corrosion inhibitors tend to be highly colored and/or opaque. An effective corrosion inhibiting pigment has throwing power and can protect exposed base metal in a scratch or flaw by oxidizing and passivating it at a distance during aqueous corrosion when dispersed in a suitable carrier phase. These compounds are usually solids or liquids that are typically dispersed in a liquid carrier or binder system such as a paint or wash. These compounds may also be used to help inhibit corrosion without a significant liquid carrier using an integral binder and/or a low-volatile application method. Barrier layer formers such as sol-gel coatings or polymeric films are also used, but they tend to have no inherent oxidizing character and no appreciable throwing power and fail to protect the metal surface when the film is breached.
[0005] Pigments that contain hexavalent chromium (CrVI) compounds are the de facto standard for high-performance corrosion inhibiting paints and coatings for metal protection and are a typical corrosion inhibitor used to protect aluminum, zinc, magnesium, iron, titanium, copper and their alloys. Zinc (C.I. Pigment Yellow 36) and strontium (C.I. Pigment Yellow 32) chromate pigments are typically used, although higher-solubility calcium and magnesium chromates have also seen some limited use as pigments. The coating vehicles of these pigments include alkyd-type primers, acrylic primers, and elastomeric sealants, among others. Some transition metal chromate pigments (e.g., complexed with copper, iron, manganese, or cobalt) and organic chromate pigments (e.g., bound with nitrogenous compounds such as guanidinium) have been used in protective coating systems. Barium or lead chromates have also been used as corrosion inhibitors, as well as colorants. Variations in chromate speciation (i.e., what the chromate ions are bound to) will result in significant differences in protection when used as corrosion-inhibiting pigments, due to differences in chromate solubility.
[0006] A clear correlation between performance and solubility of chromate pigments has been shown. However, oxidizing chromates can be dangerous to use as corrosion inhibitors if they are not delivered in sufficient quantity in a timely manner to the location of a coating breach. The chromate composition was far more important to the corrosion inhibiting performance of the primer film than the organic coating composition.
[0007] A principle use of zinc and strontium chromate pigments is in wash- or etch-primer formulations for aluminum protection. Wash- or etch-primers, which have been used since the 1940s, represent one of the harshest application conditions for chromate pigments. Wash-primers are applied to metal surfaces under acidic conditions where the primer is cured as a corrosion inhibiting film. Chromate pigment powders dispersed in an alcohol/resin base mixture are combined with an aqueous phosphoric acid diluent solution. The acid roughens the metal surface and initiates cross-linking of the resin to form a pigment-filled polymeric film. The chromate pigment may also be dispersed in other carriers that are not as harsh as the wash primer. However, if a corrosion-inhibiting pigment can survive the harsh conditions of acid diluent, then it can usually be successfully incorporated within other paint, polymeric, or barrier film systems for corrosion inhibition.
[0008] An important use of chromate pigments is in coil coating formulations for steel, zinc-coated steel, or aluminum sheet stock. Coil coatings can represent a challenging application environment for pigments in that cure temperatures for these paints can exceed 100 C. Corrosion-inhibiting pigments for these applications must exhibit both throwing power to inhibit corrosion and be thermally stable at elevated temperatures when incorporated into the paint.
[0009] Lead chromate pigments of various compositions are mostly used as colorants, although they are also used for corrosion protection, albeit often for different applications than zinc or strontium chromates. This is necessitated by the much lower solubility of lead chromate in comparison to these other chromates. The dark yellow lead chromate (PbCrO4, C.I. Pigment Yellow 34) exhibits a solubility of approximately 10−7 moles/liter Cr+6, whereas the darker basic lead chromate (PbCrO4.PbO, C.I. Pigment Orange 21) exhibits slightly lower solubility in water. In addition, lead chromate can be combined with other lead compounds to alter the spectral or solubility characteristics. For example, the lemon yellow lead silicochromate (PbCrO4.PbSiO3) and reddish lead molybdate-chromate (PbCrO4.PbMoO4, C.I. Pigment Red 104) are representative examples. [Note: This same situation exists for zinc chromate pigments such as ZnCrO4, ZnCrO4.Zn(OH)2, and ZnCrO4(OH).Zn(OH)2, wherein increased basicity leads to lowering of the solubility.]
[0010] While lead chromate can be used in some of the same coating vehicles as zinc or strontium chromate (i.e., alkyd-type primers), the much lower solubility of lead chromate permits its use in binder systems for which zinc or strontium chromate would be unsuitable. For example, lead chromate is often used in oil-based paints (i.e., linseed oil) wherein greater than 75% by weight of the paint system is pigment. The mechanistic action of the divalent lead ion present in the lead chromate pigments is discussed below.
[0011] Pigments that contain tetravalent lead (PbIV) are also used extensively in coatings for metal protection, especially for steels and cast irons. The most notable PbIV pigment is red lead (Pb3O4, C.I. Pigment Red 105). Red lead is compositionally equivalent to lead plumbate [(Pb2+)2(PbO444−)], wherein only one of the constituent lead atoms is in the tetravalent oxidation state, while the other two are present as the more common divalent species. The PbVI solubility for this compound is a remarkably low 10−17 moles/liter Pb+4 (Glasstone, J. Chem. Soc. 121: 1456-69, 1922), implying an extremely low release rate of PbIV. Red lead is used primarily in alkyd-type primers as well as oil-based paints such as those containing linseed oil.
[0012] Calcium plumbate (Ca2PbO4, Caldiox™) is another representative example of a corrosion-inhibiting pigment containing PbIV. Due to its higher solubility in comparison to red lead, calcium plumbate is most frequently used for applications where a quicker release of oxidizing ions is necessary for protection, such as on galvanized steel. Calcium plumbate is most frequently used in alkyd-type or acrylic primers.
[0013] The use of hexavalent chromium or tetravalent lead pigments allows a broad range of service conditions to be addressed by tailoring the solubility of the pigment to the application needs. Very low solubility pigments, such as red lead, employ other corrosion-inhibiting mechanisms in addition to oxidative passivation. The divalent lead ions present in red lead (and even lead chromate) have been observed to form “lead soaps” after long storage when the pigment is used in conjunction with oil paints, especially those comprised of linseed oil. “Lead soaps” are reaction products between the alkaline divalent lead ions and the long-chain carboxylic acids present (i.e., oleates, linoleates, linolenates, palmitates, and stearates). This indicates that even though these pigments exhibit low solubility in water, the constituent ions are still chemically active, but less than their more soluble cousins. The divalent lead ions form insoluble compounds with corrosive anions such as sulfate, and low-solubility compounds with other corrosive ions such as chloride, thereby effectively removing them from the corroding system. For the heavier, more insoluble lead pigments such as red lead and basic lead chromate, the inhibiting action is due to both the oxidative tetravalent lead or hexavalent chromium ions, and the ability of the divalent lead ions to ‘capture’ (insolubilize) corrosive anions such as sulfate.
[0014] Significant efforts have been made in government and industry to replace CrVI and PbIV with other metals for corrosion-inhibiting applications due to toxicity, environmental, and regulatory considerations. An effective replacement for hexavalent chromate or tetravalent lead pigment needs to have throwing power for self-healing coating breeches. Throwing power is the ability of a highly oxidized ion, such as hexavalent chromium or tetravalent lead, to oxidize and passivate the exposed bare metal in a small scratch or flaw.
[0015] A number of materials have been introduced as corrosion-inhibiting replacement pigments for tetravalent lead- or hexavalent chromium-based compounds. Commercially available corrosion inhibiting pigments including compounds such as molybdates, phosphates, silicates, cyanamides, and borates that have no inherent oxidizing character have been used as alternatives to chromate pigments. Coatings that contain these materials can effectively inhibit corrosion as barrier films until the coating is breached, as by a scratch or other flaw. Films or coatings that do not contain oxidizing species can actually enhance corrosion on a surface after failure due to the effects of crevice corrosion.
[0016] Manganese is one non-toxic, non-regulated metal which has been considered as a chromium or lead replacement. Manganese (like chromium or lead) exhibits more than one oxidation state (Mn+2, Mn+3, and Mn+4). In addition, the oxidation-reduction potential is comparable to that of CrVI or PbIV in acidic solutions. For example, in acid solution:
Mn+3+e−Mn+2+1.49 V
Mn+4+e−Mn+3+1.65V
Cr+6+3e−Cr+3+1.36 V
Pb+4+2e−Pb+2+1.70 V
[0017] The MnIV and MnIII ions are very good oxidizing species with oxidation-reduction potentials of +1.65 V and +1.49 V (at pH 0), respectively. The hydroxyl and oxygen liberated from water when MnIV or MnIII is reduced will oxidize nearby bare metal. This results in a passivated metal surface if sufficient oxygen is released. The potential required to reduce tetravalent or trivalent manganese to divalent manganese is only 0.29 or 0.13 volts greater than that needed to add three electrons to reduce CrVI to trivalent chromium (CrIII). Although neither MnIV or MnIII match PbIV in terms of redox potential, neither is significantly lower and so comparable passivation of metal is achieved. MnII is formed during corrosion inhibition by the oxidation of base metal in the presence of MnIV or MnIII and water. MnII is similar to CrIII in that neither is particularly effective as redox-based corrosion inhibitors.
[0018] A number of pigments using manganese have been reported in the literature over the years, but none approach the general performance or utility of PbIV- or CrVI-based pigments. For example, Manganese Violet is a colorant composed of MnII pyrophosphate with no oxidizing characteristics.
[0019] A number of compounds have been described as corrosion-inhibiting agents, including organic mercapto and thio compounds, cyclic tetraaza compounds, aminophosphonic acid, and triazinedithiols and triazinetrithiols. Other compounds have been described as corrosion inhibiting when complexed with manganese, typically in the divalent charge state. Among these compounds are porphyrin derivatives, tetraaza organic compounds, phosphoric and phosphonic acids, naphthenates, amidosulfonic acids, and amino acids. However, the pigments formed from these compounds provide only limited corrosion protection and do not approach the benefit derived from the use of hexavalent chromium.
[0020] In addition, the formation of manganese-containing pigments in which the manganese is complexed with ligands such as hydrazones, O bidentates, azomethines, phthalocyanines, azo and disazo complexes, N—S bidentates, oximes, tetraaza complexes, porphyrins, 1,2-dithiolates, and semicarbazones, has also been described. However, these compounds do not use tetravalent or trivalent manganese and are not used for anticorrosive applications.
[0021] U.S. Pat. No. 6,416,868 to Sullivan, et al. describes the use of alkaline earth-manganese oxides as pigments, wherein the alkaline earth is selected from Mg, Ca, Sr, and Ba. The pigments are described as being colorants and as resisting heat build-up due to infrared reflectance. Corrosion inhibiting characteristics of these compositions are not discussed or claimed. Additional manganese-containing colorants, frits, and ceramic pigments with no discussed or claimed anticorrosive properties are identified in U.S. Pat. No. 4,159,207 to Nuss, U.S. Pat. No. 3,832,205 to Lowery, and U.S. Pat. No. 5,254,162 to Speer, et al., and German Patent Nos. DE 4131 548 and DE 40 02 564, both to Speer, et al.
[0022] U.S. Pat. No. 4,469,521 to Salensky describes a corrosion-inhibiting pigment formed by sintering manganomanganic oxide (Mn3O4) with oxides of calcium, zinc, barium, magnesium, or strontium.
[0023] U.S. Pat. No. 4,388,118 to Eppler describes a corrosion-inhibiting black pigment formed by calcining calcium or strontium oxides or carbonates with manganese oxides. The formed calcium manganese oxide or strontium manganese oxide pigments have very low oil absorption and high tint strength.
[0024] German Patents Nos. 26 42 049, 28 15 306, and 26 25 401 to Hund, et al. describe the use of calcined calcium/iron/aluminum/manganese oxides as corrosion-inhibiting pigments.
[0025] Manganese oxides themselves have been described as being constituents in corrosion-inhibiting formulations. For example, U.S. Pat. Nos. 4,417,007 and 4,417,008 to Salensky, et al. as well as Belgian Patent Nos. BE 893,677 to Chopra, et al. and BE 893,676 to Salensky, et al. describe manganomanganic oxide (Mn3O4) as a constituent in a solvent-based paint formulation comprised of resin binders and additional extenders, fillers, and solvents. Manganese dioxide (MnO2) is also described as an anticorrosive constituent within formulations in French Patent No. 2,348,257 to Zatmann and German Patent No. DE 39 35 478 to Ortlepp.
[0026] U.S. Pat. No. 4,788,411 to Skinner describes a paint composition described to prevent corrosion of welds. This composition is described as being composed primarily of zinc dust, with manganomanganic oxide (Mn3O4) and organic binder included. The zinc pigment is described as being especially important for corrosion protection.
[0027] To date, no truly effective replacements have been developed for pigments based on CrVI or PbIV. Accordingly, the need remains for improved corrosion-protective pigments composed of currently unregulated and/or nontoxic materials which have an effectiveness, ease of application, and performance comparable to current CrVI or PbIV pigment formulations, and for methods of making and using the same.
SUMMARY OF THE INVENTION[0028] This need is met by the present invention which represents a significant improvement in the formulation of non-toxic pigments through the use of trivalent or tetravalent manganese. Although the present invention is not limited to specific advantages or functionality, it is noted that the trivalent and/or tetravalent manganese pigments of the present invention have been demonstrated with accelerated corrosion testing to retard corrosion to a higher degree than prior art manganese pigments and other alternatives to CrVI- or PbIV-based corrosion inhibiting pigments. These pigments have been tested to inhibit corrosion to the same degree as zinc, strontium, and lead chromate-based CrVI pigments, as well as red lead or calcium plumbate Pb IV pigments. The raw materials are not exotic, are relatively inexpensive, and do not require complicated synthesis methods.
[0029] The present invention utilizes “valency stabilization” of the trivalent or tetravalent manganese ion in the as-formed pigments to achieve corrosion resistance comparable to the more soluble chromate-based CrVI pigments. More specifically, in order to achieve a high degree of corrosion resistance, a MnIII-based or MnIV-based pigment must exhibit the following characteristics:
[0030] 1) A corrosion inhibiting pigment must contain a suitable source of oxidizing species. These species quickly oxidize bare metal and form a protective surface if bare metal is exposed in a coating breach.
[0031] 2) A valence stabilizer for the trivalent or tetravalent manganese ion is necessary to ensure that the ion will not be reduced too quickly to the divalent state when released into solution or in the coating. The importance of stabilizing the manganese ion in its trivalent or tetravalent charge state was not previously recognized as critical to the corrosion inhibiting function of a pigment.
[0032] 3) The MnIII or MnIV pigment powder must be a “sparingly soluble”, “low solubility”, or “insoluble” compound in water when dispersed in its binder-carrier system. If the pigment is too insoluble in a selected coating system that requires inhibitor release, an insufficient amount of corrosion inhibitor will be delivered to a flaw. A poorly formed, incomplete oxide layer produced by a pigment of too low solubility for a given binder-carrier system will not only fail to inhibit corrosion, but can promote crevice corrosion and result in locally enhanced corrosion rates.
[0033] The reservoir of oxidizing ions can be quickly flushed away if the pigment is too soluble, and typical corrosion will begin. Highly soluble pigments are also known to result in osmotic blistering of paint films and coatings. Trivalent or tetravalent manganese pigments that are too soluble can also be responsible for osmotic blistering depending on the aqueous permeability the carrier film.
[0034] It is difficult to place specific solubility values to these optimum “sparingly soluble”, “low solubility”, or “insoluble” pigment materials because there appear to be several variables associated with what makes an optimum anticorrosive pigment material (e.g., specific resin/binder system in which it is placed). The particle size and particle shape has been observed to noticeably affect the solubility of “low solubility” pigments such as lead chromate (e.g., May and Kolthoff, J. Phys. & Colloid Chem. 52: 836-54, 1948). The solubility of the candidate trivalent or tetravalent manganese pigment must be matched to the hexavalent chromium or tetravalent lead pigment that it is replacing (Table 1), such as zinc or strontium chromate, or calcium plumbate. If the trivalent or tetravalent manganese pigment exhibits a solubility in water of between about 1×10−4 and about 1×10−1 moles per liter of trivalent or tetravalent manganese, then appreciable corrosion inhibition will be observed in the binder systems that typically incorporate zinc or strontium chromates (or calcium plumbate). Pigments that incorporate stabilized trivalent or tetravalent manganese compounds that fall outside of this particular range may also exhibit some corrosion inhibition as zinc or strontium chromate (or calcium plumbate) replacements. For example, pigments with solubilities as high as 1×100 moles per liter or as low as 1×10−5 moles per liter of trivalent or tetravalent manganese at standard temperature and pressure (about 25° C. and about 760 Torr) will exhibit some corrosion resistance in binder systems that currently incorporate zinc or strontium chromate (or lead plumbate), although not as great as those compounds which fall within the optimum solubility range. A solubility range from 1×10−6 to 1×10−8 moles per liter trivalent or tetravalent manganese is desirable for manganese pigments to inhibit corrosion in binder systems where lead chromate pigments are currently used. Pigments that incorporate trivalent or tetravalent manganese that fall slightly outside of this range may also inhibit corrosion as lead chromate replacements. For example, pigments with solubilities as high as 1×10−5 moles per liter or as low as 1×10−9 moles per liter of trivalent or tetravalent manganese at standard temperature and pressure (about 25° C. and about 760 Torr) will exhibit some corrosion resistance in binder systems that currently incorporate lead chromate, although not as great as those compounds which fall within the optimum solubility range. Lastly, any trivalent or tetravalent manganese pigment that exhibits a solubility lower than 1×10−9, but higher than 1×10−17 (based on red lead solubility) moles per liter of trivalent or tetravalent manganese at standard temperature and pressure (about 25° C. and about 760 Torr) will exhibit some corrosion resistance in binder systems that currently incorporate red lead. Under special conditions (i.e., very carefully controlled particle sizes), trivalent or tetravalent manganese compounds with solubilities as high as 1×10−7 moles per liter trivalent or tetravalent manganese can be used as red lead replacements. The solubility characteristics of the trivalent or tetravalent manganese in the pigment can be controlled through the use of valence stabilizer materials that form compounds that fall within the desired solubility ranges. A “controlled release” of trivalent or tetravalent manganese can thus be achieved similar to the “timed release” of hexavalent chromium or tetravalent lead in the “state-of-the-art” systems. 1 TABLE 1 Solubility Ranges for Trivalent and/or Tetravalent Manganese Replacements for Hexavalent Chromium or Tetravalent Lead Pigments Hexavalent Chromium Optimum Solubility Acceptable Solubility or Tetravalent Lead Range (moles/L Range (moles/L Pigment to be Replaced Mn+3 and/or Mn+4) Mn+3 and/or Mn+4) Zinc Chromates 1 × 10−1 (upper) 1 × 100 (upper) (including basic forms) to to Strontium Chromates 1 × 10−4 (lower) 1 × 10−5 (lower) Calcium Plumbate Lead Chromates 1 × 10−6 (upper) 1 × 10−5 (upper) (including basic forms) to to Lead Molybdate-Chromate 1 × 10−8 (lower) 1 × 10−9 (lower) Lead Silicochromate Red Lead 1 × 10−9 (upper) 1 × 10−7 (upper) to to 1 × 10−17 (lower) 1 × 10−17 (lower)
[0035] 4) The “valence stabilizer” optionally helps establish an electrostatic barrier layer around the cation-stabilizer compound in aqueous solutions. The nature and character of the electrostatic double-layer surrounding the cation-stabilizer compound may be controlled and modified by careful selection of stabilizer species. In general, the electrostatic double layer formed acts to protect the cation from premature reaction with hydronium, hydroxide, and other ions in solution. The formation of electrostatic barrier layers also helps to impede the passage of corrosive ions through the binder phase to the metallic surface.
[0036] 5) The trivalent or tetravalent manganese pigment material may also exhibit ion exchange behavior towards corrosion promoting ions, particularly alkali species. This optional consideration can be important because alkali ions are aggressive aqueous corrosion enhancers in alloys which contain metals such as aluminum, magnesium, or zinc.
[0037] 6) The manganese/valence stabilizer complex can optionally exhibit a color change between the trivalent or tetravalent and divalent manganese oxidation states. This color change can act as a metric to determine when the “throwing power” associated with the pigments is no longer available, and when the paint system in which it is contained needs to be replaced. For this reason, it is also optionally important that the color of these pigments that exhibit a color change between divalent and trivalent or tetravalent oxidation states that is light-fast (i.e., not changed by strong light).
[0038] The effectiveness of an oxidizing species is a function of its individual oxidation-reduction potential, and more highly oxidized species exhibit greater corrosion protection, although lower stability. A stabilizer is necessary to provide a timed release of the inhibitor ion, as well as being needed to ensure that the oxidative strength will not be reduced too rapidly. Thus, a valence stabilizer is required for the trivalent or tetravalent manganese ion because of its reactivity and to produce controlled trivalent or tetravalent manganese solubilities. The corrosion resistance of a number of aluminum alloys as tested using both ASTM B-117 and ASTM G-85 has been enhanced through the use of stabilized trivalent and/or tetravalent manganese pigments. Not only do these optimized pigments retard corrosion to a higher degree than other prior art manganese pigments, but their corrosion resistance is comparable to that of hexavalent chromium or tetravalent lead systems.
[0039] In one aspect, the invention comprises a mechanistic and chemical approach to the production of corrosion-inhibiting pigments using trivalent or tetravalent manganese. This approach uses stabilizer materials which form compounds with trivalent or tetravalent manganese that match the observed solubilities of hexavalent chromium or tetravalent lead pigments currently in use (see Table 1). The solubility ranges reported provide a release of trivalent or tetravalent manganese at a rate slow enough that most binder systems will provide protection for an extended period of time and fast enough to inhibit corrosion during conventional accelerated corrosion testing methods such as ASTM B-117 and G-85. Compounds that fall slightly outside of the solubility ranges shown in Table 1 may also provide some corrosion-inhibiting activity under certain conditions and binder systems. However, pigment compounds with aqueous solubilities far outside of the target ranges are likely to be inefficient corrosion inhibitors. Solubility control can be achieved using organic or inorganic stabilizer materials.
[0040] In an optional aspect, the invention is the achievement of corrosion-resistant pigments using trivalent or tetravalent manganese by the use of stabilizer materials which form compounds that exhibit electrostatic dipoles to form electrostatic barrier layers composed of ions such as hydronium (H3O+) or hydroxide (OH−) in the presence of water. The formation of these electrostatic barrier layers through the use of stabilizer materials can be achieved using organic or inorganic materials.
[0041] In another optional aspect, the invention is the achievement of corrosion-resistant pigments using trivalent or tetravalent manganese by the use of stabilizer materials which form compounds that exhibit ion exchange behavior towards alkali ions. The formation of this ion exchange behavior can be achieved through the use of organic or inorganic materials.
[0042] In yet another optional aspect, the decomposition temperature of the trivalent or tetravalent manganese/valence stabilizer complex upon which the pigment is based should be above 100° C. In addition, the melting temperature of the complex is typically above 50° C., although lower-melting complexes may have some applications.
[0043] In still another optional aspect, the manganese/valence stabilizer complex upon which the pigment is based should exhibit a color change between the trivalent or tetravalent and divalent oxidation states. This allows for a visual metric of when the pigment has lost its “throwing power”, and the binder system within which it is contained must be replaced. Therefore, it is desirable that the color of these pigments be light-fast (unchanged by exposure to strong light).
[0044] These MnIII and MnIV compounds represent a substantial performance improvement over prior art related to pigment alternatives used to replace CrVI-based and PbIV-based corrosion inhibiting pigments. They also provide a capability to tailor the corrosion inhibiting pigment to the carrier system. This allows current binder/resin systems used for chromates or plumbates to be used for MnIII- or MnIV-based systems without modification. Likewise, new binder/carrier/resin systems with improved physical properties can be developed without the restriction of compatibility with zinc, strontium, or lead chromate; or plumbate pigments.
[0045] The raw materials needed for the solutions used to form these coatings are relatively inexpensive. The pigments do not use exotic materials or require complicated synthesis methods.
[0046] Accordingly, it is an object of the present invention to provide non-toxic, corrosion-protective pigments based on trivalent or tetravalent manganese and for methods of making and using the same. These and other objects and advantages of the present invention will be more fully understood from the following detailed description of the invention. It is noted that the scope of the claims is defined by the recitations therein and not by the specific discussion of features and advantages set forth in the present description.
DETAILED DESCRIPTION OF THE INVENTION[0047] A. Starting Materials
[0048] Four general starting materials are used for the preparation of trivalent or tetravalent manganese corrosion-inhibiting pigments. These include a manganese source, an oxidation source (if the precursor is a divalent manganese salt), a valence stabilizer source, and optional additional solubility control agents.
[0049] 1) Manganese Source
[0050] Manganese is a nontoxic, non-regulated replacement metal for chromium or lead that exhibits more than one oxidation state (MnII, MnIII, and MnIV). The oxidation reduction potential for MnIII-MnII is comparable to that of the CrVI-CrIII couple, and the oxidation-reduction potential for MnIV-MnIII is comparable to the PbIV-PbII couple. The ionic radii of MnIII (61 pm) and MnIV (54 pm) are slightly larger than the CrVI ion (44 pm), and they will have a correspondingly lower charge density (electrostatic field) per ion as compared to hexavalent chromium. Conversely, both MnIII and MnIV are smaller than PbIV (78 pm), and have a higher charge density (electrostatic field) per ion compared to tetravalent lead. These factors are important in the selection and design of trivalent or tetravalent manganese compounds that match or exceed the performance of hexavalent chromium or tetravalent lead pigments.
[0051] Unlike most other high valence metal (HVM) systems, trivalent and/or tetravalent manganese ions exhibit remarkable stability under many environmental conditions. The numerous examples of manganese minerals that contain MnIII or MnIV are evidence of this stability (see Table 2 below). Trivalent or tetravalent manganese-containing minerals could conceptually be used as corrosion-inhibiting pigments. (However, natural impurities contained therein would alter the compositions so that the pigment materials would exhibit altered solubility characteristics.) The trivalent or tetravalent manganese minerals shown in Table 2 could be used as precursors for the production of anticorrosive manganese pigments for lead chromate or red lead replacements. 2 TABLE 2 Naturally-Occurring Trivalent and/or Tetravalent Manganese-Containing Minerals Useful as Feedstock for Anticorrosive Manganese Pigment Production Manganese Approximate Valence Crystal Mineral Composition State(s) Structure Pyrolusite MnO2 +4 Tetragonal Hausmannite Mn3O4 +3/+2 Tetragonal Manganite MnO(OH) +3 Tetragonal Ramsdellite MnO2 +4 Orthorhombic Bixbyite Mn2O3 +3 Cubic Groutite MnO(OH) +3 Orthorhombic Feitknechite MnO(OH) +3 Tetragonal Akhtenskite MnO2 +4 Hexagonal Buserite MnO2 +4 Unknown Nsutite Mn(O,OH)2 +4/+3 Hexagonal Hetacrolite ZnMn2O4 +3 Tetragonal Marokite CaMn2O4 +3 Orthorhombic Hydro- HZnMn2−xO4 +3/+2 Tetragonal hetaerolite Braunite Mn7SiO12 +3/+2 Tetragonal Psilomelane (Ba,H2O)2Mn5O10 +4/+3 Monoclinic (aka Roman- echite) Crypt- KMn8O16 +4/+3 Monoclinic or omelane Tetragonal Manjiroite (K,Na)Mn8O16 +4/+3 Tetragonal Lithiophorite (Al.Li)MnO2(OH)2 +4/+3 Hexagonal Chal- (Zn,Fe,Mn)Mn3O7 +4 Rhombohedral cophanite Hollandite (Ba,K,Na)Mn8(O,OH)16 +4/+3 Unknown Woodruffite (Zn,Mn)Mn3O7 +4 Tetragonal Neltnerite CaMn6SiO12 +3 Tetragonal Birnessite Na4Mn14O27 +4/+3 Hexagonal Asbolane (Ni,Co)xMn(O,OH)4 +4/+3 Hexagonal Todorokite (K,Ca,Na)(Mn,Al,Mg)6O12 +4/+3 Monoclinic Vernadite (Mn,Fe,Ca,Na)(O,OH)2 +4/+3 Hexagonal
[0052] a) Manganese Sources for “Sparingly Soluble” Pigments
[0053] Zinc and strontium chromates, as well as calcium plumbate, are “sparingly soluble” in water, and are typically formed via precipitation from a liquid media (i.e., water), with subsequent particle sizing and powder processing. Trivalent or tetravalent manganese pigments to be used for the same applications as zinc and strontium chromates, or calcium plumbate, are produced in a similar fashion. This is because the higher solubility requirements (1×10−1 to 1×10−4 moles/liter inhibitor ion) for these pigments necessitate much higher release rates of MnIII or MnIV than can typically be achieved by calcined or “fired” materials. MnIII or MnIV compounds that can achieve high solubilities and release rates require special valence stabilizer and/or solubility control agents. The easiest preparative method for these constituents is via precipitation processes.
[0054] Manganese precursors for “sparingly soluble” pigments can be nearly any water, alcohol, or hydrocarbon soluble manganese compound in which the manganese is in the divalent, trivalent, tetravalent, or heptavalent oxidation state. Water-soluble precursors are typically used. Inorganic divalent manganese precursor compounds include, but are not limited to, manganese nitrate, manganese sulfate, manganese perchlorate, manganese chloride, manganese fluoride, manganese bromide, manganese iodide, manganese bromate, manganese chlorate, and complex fluorides such as manganese fluosilicate, manganese fluotitanate, manganese fluozirconate, manganese fluoborate, and manganese fluoaluminate. Organometallic divalent manganese precursor compounds include, but are not limited to, manganese formate, manganese acetate, manganese propionate, manganese butyrate, manganese valerate, manganese benzoate, manganese glycolate, manganese lactate, manganese tartronate, manganese malate, manganese tartrate, manganese citrate, manganese benzenesulfonate, manganese thiocyanate, and manganese acetylacetonate.
[0055] The manganese precursor for “sparingly soluble” pigments may also be a compound with manganese already in the trivalent or tetravalent oxidation state. A representative example is manganese III acetylacetonate. The manganese precursor for “sparingly soluble” pigments may be a compound with the manganese in the heptavalent oxidation state (permanganates). Heptavalent manganese precursors include, but are not limited to: potassium permanganate, sodium permanganate, lithium permanganate, ammonium permanganate, magnesium permanganate, calcium permanganate, strontium permanganate, barium permanganate, zinc permanganate, ferric permanganate, nickel permanganate, copper permanganate, cobalt permanganate, cerium permanganate, lanthanum permanganate, yttrium permanganate, and aluminum permanganate.
[0056] b) Manganese Sources for “Low Solubility” or “Insoluble” Pigments
[0057] Lead chromates are typically formed via precipitation from aqueous solution, while red lead pigments are produced by firing PbII oxide (PbO) in an oxidizing environment at approximately 400° C. Trivalent or tetravalent manganese compounds to be used as lead chromate or red lead replacements can be formed in two ways: 1) precipitating a manganese compound from a liquid medium and then firing or calcining the resultant precipitate; or 2) calcining or firing a manganese-containing compound or mixture using insoluble precursors. The commonality between these two options is firing, calcining, or otherwise heating a manganese-containing compound or mixture. The only manganese compounds suitable as replacements for lead chromate or red lead pigments (<1×10−5 moles/liter inhibitor ion) are those produced by calcining or heating manganese compounds with or without other additives.
[0058] Soluble manganese sources for precipitation prior to calcining, firing, or otherwise heating are similar to those described above for “sparingly soluble” pigments. Insoluble manganese-containing compounds useful as precursors include MnII, MnIII, MnIV, and some MnIV compounds. Insoluble divalent manganese compounds useful as precursors include, but are not limited to: manganese oxide (manganosite), manganese hydroxide (pyrochroite), manganese carbonate (rhodochrosite), manganese silicate (rhodonite, tephroite, manganhumite, or manganjustite), manganese sulfide (alabandite or hauerite), manganese phosphate (reddingite or hureaulite), manganese oxalate, and manganese borate. Insoluble trivalent manganese or tetravalent manganese compounds suitable as precursors include manganese dioxide (MnO2), manganomanganic oxide (Mn3O4), manganese sesquioxide (Mn2O3), lithiated manganese spinel (LiMn2O4), and manganese III hydroxide (MnOOH). The MnIII and MnIV containing minerals described in Table 1 are also useful insoluble trivalent and tetravalent manganese precursors.
[0059] MnIII and MnIV are capable of providing corrosion protection at a distance to a metal surface in the presence of coating flaws such as scrapes, scratches, and holes because of their throwing power. The solubility of the MnIII or MnIV compound needs to be tailored to suit the needs of the protection system and must be neither too high, nor too low in that system. The protective system includes the binder phase, assorted modifiers, and under- and over-coatings. The system needs to be performance matched to its intended usage environment. Timely release and throwing power of the inhibitor are critical to protective performance, but controlled tailoring of these has not been taught in prior art. Likewise, the body of systematic chemistry data required to control these properties has not been readily available in a form useful to help design coatings. The present invention outlines how to stabilize MnIII and MnIV with a variety of materials so the MnIII and MnIV may be adapted to a multitude of pigment applications with specific compatibility requirements.
[0060] 2) Oxidation Source
[0061] If MnIII and/or MnIV pigment compounds are produced via precipitation, an oxidizing species will typically be included in the synthesis solution if divalent manganese compounds are used as precursors for MnIII and MnIV. Otherwise, a post-precipitation oxidation step will be required. Additional amounts of oxidizer may be added to help control and maintain a desired amount of MnIII/MnIV in the pigment solution by reoxidizing MnIII/MnIV that has become reduced. The trivalent manganese ion is an exceptionally good oxidizing species with an oxidation-reduction potential of +1.49 V at a pH of 0 for the MnIII-MnII couple in water, and the tetravalent manganese ion is an even stronger oxidizing species, with a redox potential of +1.65 V under similar conditions. Strong oxidizers are required because of the high potential of their redox reaction. The oxidizers may be gases, liquids, or solids. Solid oxidizers are typically used for this application due to ease of handling and reagent measurement. Other starting materials (manganese source and stabilizer source) will also frequently be solids. Liquid oxidizers may be used, but handling and accurate process metering have proven difficult. Gaseous oxidizers may be the most cost effective and chemically efficient on a large scale, but are also the most problematic due to handling and venting concerns.
[0062] Oxidizers suited for the purpose of producing and maintaining the manganese ion in the trivalent or tetravalent charge state include but are not restricted to peroxides and peroxo compounds (including superoxides, persulfates, perborates, pernitrates, perphosphates, percarbonates, persilicates, peraluminates, pertitanates, perzirconates, permolybdates, pertungstates, pervanadates, and organic peroxyacid derivatives), ozone, hypochlorites, chlorates, perchlorates, nitrates, nitrites, vanadates, iodates, hypobromites, chlorites, bromates, permanganates, periodates, and dissolved gases such as oxygen, fluorine, or chlorine. Inorganic and organic derivatives of these compounds may be used. Typical oxidizers for this use are peroxides, persulfates, perbenzoates, periodates, bromates, hypochlorites, gaseous dissolved oxygen, and even the oxygen content of air. In general, any inorganic, organic, or combination species with an oxidation potential of +1.0 V or greater (at a pH of 1) will be capable of oxidizing divalent manganese to the trivalent or tetravalent oxidation state.
[0063] Oxidized manganese may also be produced in solution by electrolytic oxidation. However, this approach may not be economically feasible due to the energy costs associated with electrolytic oxidation. Chemical oxidation, such as that described above, currently offers the best-value approach for oxidizing manganese to the trivalent or tetravalent state.
[0064] It is also possible to produce a divalent manganese/valence stabilizer complex, and then apply an oxidizer to oxidize divalent manganese to trivalent or tetravalent manganese. This, however, is less typical because the percentage of trivalent or tetravalent manganese will decrease from the outside to the interior of the pigment particle.
[0065] Oxygen (including the oxygen content of air) is the most useful oxidizer source for the production of “low solubility” or “insoluble” trivalent or tetravalent manganese pigment compounds via calcining, firing, or otherwise heating processes. The control of temperature, partial pressure of oxygen, flowrate, and even particle size allows the oxidation state of the manganese in the sintered particle to be divalent, trivalent, or tetravalent. Other oxidizing gasses such as NOx, SOx, chlorine, fluorine, or ozone can also be used, but these are less desirable due to their environmental impact.
[0066] 3) Valence Stabilizers
[0067] Manganese is effective as an oxidative corrosion inhibitor if it can be supplied in sufficient quantities in the trivalent and/or tetravalent charge-state when brought into contact with unprotected bare metal. Corrosion resistance comparable to that of CrVI or PbIV can be achieved by the use of MnIII and/or MnIV oxidizer ions in pigment compounds. Valence stabilizers are materials that, when assembled, modify the rate of reduction and the solubility of the MnIII and/or MnIV ions. Valence stabilization has not been previously recognized as an important consideration in the development of effective corrosion inhibiting pigments. Stabilization helps avoid reduction and premature conversion of the ion to the divalent charge-state during compound formation, carrier incorporation, application, and exposure to a corrosive environment. Stabilizers control solubility, mobility, ion exchange, binder compatibility, and the degree of surface wetting. The exact solubility of this compound may be modified by species released into solution by the dissolving metal surface or by the subsequent addition of solubility control agents. A variety of inorganic and organic stabilizers are available that can serve to control solubility. The stabilizer may also act as an ion-exchange host and/or trap for alkali or halide ions in solution.
[0068] Valence stabilization is necessary for MnIII and MnIV due to the reactivity of these ions with water. Unlike MnII, which can readily be solubilized in water, MnIII and MnIV ions rapidly react with water, producing elemental oxygen. Valence stabilization is particularly useful for the more soluble MnIII and MnIV compounds (i.e., >1×10−5 moles/liter of inhibitor ion) where more rapid release rates of these ions are necessary. For example, manganese dioxide (MnO2) is reported to exhibit a solubility in water between 2.4×10−5 and 4.0×10−7 moles/liter Mn+4, depending upon pH (Swain, et al., Anal. Chem. 47(7): 1135-7, 1975 and Savenko, Geokhimiya (3) pp. 416-9, 1985). Similarly, manganese sesquioxide (Mn2O3) is reported to exhibit a solubility in water between 3.3×10−8 and 5.1×10−9 moles/liter Mn+3, depending upon temperature (Ampelogova, et al., Radiokhimiya 31(4): 160-5, 1989). For these low solubility compounds, oxygen (O) is a satisfactory “valence stabilizer” to achieve the desired solubilities and release rates. Specialized valence stabilizers are necessary for MnIII and MnIV compounds of solubilities higher than 1×10−5 moles/liter Mn+3 or Mn+4.
[0069] The need for “valence stabilization” of trivalent or tetravalent manganese for corrosion inhibition has only been indirectly noted in the general corrosion literature as a synergistic enhancement. Corrosion inhibition behavior of nitrogen-containing organics such as aniline or pyridine has been reported to be enhanced with the addition of manganese. The exact nature of this “synergistic enhancement” has never been adequately explained. These “synergistic” mixtures of nitrogen-containing organics and manganese have also been described as being “oxygen-scavengers”, and the organics are frequently observed to “chemisorb” onto the substrate piece being protected.
[0070] This enhancement can be explained by the “valence stabilization” model of corrosion inhibition by trivalent or tetravalent manganese outlined here. Nitrogen-containing organics and manganese result in the formation of an organometallic complex where the central manganese ion can be stabilized in a higher oxidation state. The observed “oxygen-scavenging” phenomenon associated with dissolved oxygen in aqueous solutions is easily explained by the oxidation of stabilized divalent manganese to the trivalent or tetravalent state. “Sparingly soluble” MnIII or MnIV complexes containing these organics are responsible for the corrosion inhibiting activity, and these organics will appear to be “adsorbed” or “chemisorbed” from solution onto the metal piece being protected due to precipitation.
[0071] The key to providing a useful source of trivalent or tetravalent manganese at a metal surface is the creation of a compound in which the MnIII or MnIV ion is shielded from premature reduction during and after pigment formation. The formation of pigments with the proper release rate of MnIII or MnIV ions is problematic because of the instability of MnIII and MnIV in solution. A valence stabilizer must assemble around MnIII or MnIV to form a compound in order to produce the active corrosion-inhibiting component in a pigment. It is difficult to place specific solubility values to these optimum sparingly soluble pigments because of the wide range of binder systems in which corrosion-inhibiting pigments are used.
[0072] In order to replace the zinc chromates, strontium chromate, or calcium plumbate pigments, a MnIII- or MnIV-stabilized compound with a solubility in water of between about 1×10−4 and about 1×10−1 moles per liter of trivalent or tetravalent manganese should exhibit appreciable corrosion inhibition when used as a primer pigment. This solubility range provides a release of trivalent or tetravalent manganese at a rate slow enough that protection will be provided for an extended period of time and fast enough to inhibit corrosion during conventional accelerated corrosion testing methods such as ASTM B-117 and G-85 for coatings that contain these pigments. Manganese compounds that fall outside of this particular solubility range may exhibit a small degree of corrosion inhibition in the binder systems that currently use the zinc or strontium chromate pigments. For example, compositions with solubilities as high as 1×100 moles per liter or as low as 1×10−5 moles per liter of trivalent or tetravalent manganese will exhibit some corrosion resistance, although they will not be as effective as those compounds within the optimum solubility range. A common MnIII compound (MnIII acetylacetonate) is too soluble to provide effective corrosion inhibition if incorporated into a binder system such as a paint. Other compounds, such as Mn3O4 as described in the prior art, will not serve as effective corrosion inhibiting pigments in the binder systems that currently use the zinc or strontium chromate pigments because they are too insoluble.
[0073] The needed solubility will be strongly dependent on the net aqueous solubility of overlying paints and coatings and their usage environment. For example, solubility tailoring would be useful in a situation where a protected substrate is suddenly immersed in seawater, or where a rubber sealant allows only limited water penetration. Adequate corrosion protection could be achieved through the formation of a trivalent or tetravalent manganese pigment compound that exhibits a higher solubility in water (e.g., 1×100 to 1×10−3 moles per liter MnIII or MnIV). A rapid release of protective trivalent or tetravalent manganese ions would happen at the expense of depleting the manganese quickly from the coating. Trivalent or tetravalent manganese pigments of lower solubilities (e.g., 5×10−5 to 1×10−3 moles per liter MnIII or MnIV) may also be useful in some situations (e.g., as paints in nearly pure deoxygenated water). The number and range of compound solubilities offered by valence stabilized MnIII and MnIV compounds allows the development of protective coating systems with broad performance and application ranges. This feature is not presently available even for CrVI based corrosion inhibiting pigments.
[0074] Any material in the synthesis bath which complexes with trivalent or tetravalent manganese (whether inorganic or organic) and which results in the formation of a MnIII- or MnIV-containing compound that exhibits solubilities within or near this solubility range can serve as a valence stabilizer for trivalent or tetravalent manganese. The assembly of a protective shell around the highly charged MnIII or MnIV and its associated oxygen and hydroxyl species can help control the rate at which the manganese is reduced and its oxygen is released. Proper selection of materials for forming the protective shell will allow solubility tailoring of the entire assembly to its intended application environment. Valence stabilizers described above may need some type of additional solubility control to optimize the performance of the trivalent or tetravalent manganese-valence stabilizer compound. Additional solubility control agents may be in the form of inorganic or organic compounds. Their use is optional rather than a requirement for effective valence stabilization and solubility control.
[0075] Trivalent or tetravalent manganese-containing compounds that are useful as replacements for lead chromate or red lead pigments require lower solubilities. A typical formula for a red lead paint is: 3 Red lead (Pb3O4) 80 wt. Percent Linseed oil 18 wt. Percent Turpentine and liquid drier 2 wt. Percent
[0076] The majority of this paint system is pigment. If the pigment in this paint system exhibited excessive solubilities for this specific application, the coating would quickly be exhausted, leaving limited protection for the underlying metal.
[0077] An optimum solubility range from 1×10−6 to 1×10−8 moles per liter trivalent or tetravalent manganese is desirable for manganese pigments to inhibit corrosion in the binder systems that lead chromate pigments currently are used in. Pigments that incorporate trivalent or tetravalent manganese that fall slightly outside of this range may also inhibit corrosion as lead chromate replacements. For example, pigments with solubilities as high as 1×10−5 moles per liter or as low as 1×10−9 moles per liter of trivalent or tetravalent manganese at standard temperature and pressure (about 25° C. and about 760 Torr) will exhibit some corrosion resistance in binder systems that currently incorporate lead chromate, although not as great as those compounds which fall within the optimum solubility range.
[0078] Any trivalent or tetravalent manganese pigment that exhibits a solubility lower than 1×10−9 moles per liter of trivalent or tetravalent manganese at standard temperature and pressure (about 25° C. and about 760 Torr) will exhibit some corrosion resistance in binder systems that currently incorporate red lead. Under special conditions (i.e., very carefully controlled particle sizes), trivalent or tetravalent manganese compounds with solubilities as high as 1×10−7 moles per liter trivalent or tetravalent manganese can be used as red lead replacements.
[0079] As with the more soluble MnIII and MnIV compounds used as zinc or strontium chromate replacements, changes in pigment solubility can be achieved through the use of additional solubility control agents.
[0080] Several variables are associated with making optimized pigments. If the pigment is too insoluble for the specific application, then insufficient trivalent or tetravalent manganese is available to inhibit corrosion. Low solubility compounds that do not provide a sufficient amount of oxidation quickly enough to a coating breach may produce an incomplete oxide layer and thus an ineffective barrier film. If the manganese pigment is too soluble, it will be washed away quickly, and an incomplete thin oxide film will form that will not provide long-term corrosion protection, or osmotic blistering of the paint system may result. The formation of spotty or patchy oxides can promote localized crevice corrosion and can result in enhanced corrosion rates at the breach.
[0081] The traditional chromate pigments are used not only in alkyd resin systems (e.g., DoD-P-15328D Wash Primers), but also in acrylic systems (e.g., MIL-P-28577B Water-Borne Acrylic Primers), and even in sulfonated rubber sealants (e.g., MIL-PRF-81733D Sealing and Coating Compound). Tetravalent lead pigments are typically used in either oil-based (i.e., linseed oil) paint systems, although some are used in alkyd resin coatings. Fortunately, it is possible to tailor the MnIII and/or MnIV valence stabilizer compound pigment systems themselves to specific binder/solvent systems using solubility (cohesion) parameters. Solubility parameters define how well an inorganic or organometallic complex will disperse in a given resin/binder system. This represents a radical departure from traditional paint systems, in which the paint systems are configured to specific pigments.
[0082] The formation of an electrostatic double layer can be important for the effectiveness of a corrosion inhibitor once it is released into solution during corrosion. There are differences in anodic and cathodic polarization, solubility, and the saturated pH of aqueous solutions of various chromate or plumbate pigments. The formation of an electrostatic double layer around the pigment while in its carrier film will not be as important as when the species is in solution. For this reason, the development of an electrostatic double layer around the pigment is an optional consideration. For example, zinc chromate pigment-filled paint does not exhibit electrochemical inhibiting behavior. The carrier film typically behaves as a water impermeable barrier and will muffle the polar character of the pigment. The hexavalent chromium pigments SrCrO4 and ZnCrO4 have very small barrier layers associated with them, but they are effective as corrosion-inhibiting pigments. Optimized solubility for MnIII- or MnIV-valence stabilizer compounds alone can result in corrosion resistance comparable to the state-of-the-art chromium pigments. The degree of polarization exhibited by the MnIII or MnIV ions will be less than the CrVI ion because of their larger ionic radius and lower charge-state, and they will not be as efficient in forming electrostatic double layers in aqueous solution. The valence stabilization of trivalent or tetravalent manganese should be optimized to achieve the highest degree of efficiency in both solubility control and polar character, in order to further enhance the corrosion resistance.
[0083] Conversely, because both the MnIII and MnIV ions are smaller than the PbIV ion, the degree of polarization exhibited by these ions will be greater than PbIV, and they will be more effective in forming electrostatic double layers in aqueous solution. In order to replace PbIV pigments, a lower degree of valence stabilization is therefore acceptable.
[0084] The nature and character of the “electrostatic double layer” surrounding the trivalent or tetravalent manganese/valence stabilizer compound may be controlled and modified by careful selection of organic or inorganic stabilizers. Characteristics such as the electrical dipole moment and the shape/conformation (for steric effects) of the stabilizer were found to influence the performance of the corrosion-inhibiting pigment. These stabilizer ions establish a protective electrostatic shell around the cation-stabilizer compound and gather additional layers of ions such as hydronium (H3O+) or hydroxide (OH−) about them. The size of the electrostatic double layer is a function of the electrostatic potential at the compound surface and is inversely proportional to the ionic strength of the surrounding solution. An electrostatic double layer will likely form in aqueous solution for compounds that can carry a charge, have a natural electrostatic dipole, or can have an induced dipole. However, these compounds do not normally act as corrosion inhibitors because they have not been optimized for that purpose.
[0085] The melting point and decomposition temperature of the pigment material are important. Trivalent or tetravalent manganese-valence stabilizer compounds that decompose below about 100° C. limit both their useful lifetimes and range of use. The melting temperature should be above about 50° C. to ensure that the liquid phase does not form during normal handling procedures. An additive may be needed for pigments with melting temperatures below about 50° C. Inert solid addendum materials need not have any inherent corrosion-inhibiting capability and are used to provide a base (support) that the pigment can absorb on or into. Oxides, phosphates, borates, silicates, and polymers are examples of support compounds that can be used. Low melting temperature pigments (below about 50° C.) can be used, but they require handling and processing different from higher melting temperature pigments. Liquid-phase corrosion inhibitors based on MnIII, MnIV, and CrVI pigments have been demonstrated to provide excellent performance as corrosion inhibitors in primer paint systems.
[0086] The corrosion-inhibiting pigments of the present invention can optionally exhibit a color change between oxidized species and divalent species. The implications of these color changes from an applications standpoint are significant. Color changes in the pigment material in use can be used as a metric to determine when the pigment no longer exhibits corrosion-inhibiting action as a result of depleting the oxidized ion. Changes in hue of the pigment can be used to determine how much service life remains for that pigment in terms of corrosion-inhibiting capacity. Valence based color change is an attribute that conventional chromate or plumbate pigments do not exhibit. The color change associated with their redox reaction of chromate or plumbate pigments is insignificant as the pigments are reduced and “depleted” of their corrosion-inhibitive capability. Thus, trivalent or tetravalent manganese/valence stabilizer combinations that exhibit these color changes are superior to chromium or lead in terms of providing an easily measured, easily observed metric to gauge remaining service life of the pigment. However, this color change should not be initiated by exposure to strong light. Light-fast pigments are therefore desirable for these indicator pigments.
[0087] The incorporation of the valence stabilizer (inorganic or organic) may optionally result in the formation of a MnIII- or MnIV-valence stabilizer compound that also exhibits ion exchange behavior towards alkali ions. This is not a requirement of the MnIII- or MnIV-valence stabilizer compound, and pigments that do not exhibit this phenomenon have been successfully demonstrated to inhibit corrosive attack. However, it is a desirable characteristic for enhanced corrosion resistance. Existing CrVI-based or PbIV-based pigment systems do not exhibit this behavior to any significant degree.
[0088] The design of suitable MnIII- or MnIV-valence stabilizer compounds allows typical and less typical stabilizers to be identified. The general classes of compounds described below represent only a first approximation of whether a specific coordination compound will provide favorable or unfavorable properties in a MnIII- or MnIV-valence stabilizer compound. Property tailoring can also take place through selection of specific anions or cations bound to the MnIII- or MnIV-valence stabilizer coordination compound. The “physiology” of inorganic stabilizers is simple because of the limited number of atoms and structural arrangements involved in their formation. The “physiology” of organic stabilizers is not as simple. An organically stabilized manganese compound may have one or more organic ligands that may have one or more bonding sites that can interact with the MnIII or MnIV ion/oxide cluster. The bonding groups can be the same or different atoms or functional groups on an individual or a variety of ligands. An organic stabilizer ligand can be modified in an unlimited number of ways to tailor its physical behavior with respect to such properties as chemical reactivity, solubility, electrostatic and polar character, and functional behavior.
[0089] It is possible to fine tune the electronic and structural characteristics of a MnIII- or MnIV-valence stabilizer compound further via substituent groups on the coordinating ligand, and/or by the selection of cations or anions to complete the charge balance of the MnIII- or MnIV-valence stabilizer compound. For example, some substituent groups have large dipole moments associated with them, which will increase the electrostatic barrier layers associated with the manganese/valence stabilizer complexes. These include: ketones (═C═O), thioketones (═C═S), amides (—C[═O]—NR2), thioamides (—C[═S]—NR2), nitrites or cyano groups, (—CN), isocyanides (—NC), nitroso groups (—N═O), thionitroso groups (—N═S), nitro groups (—NO2), azido groups (—N3), cyanamide or cyanonitrene groups (═N—CN), cyanate groups (—O—CN), isocyanate groups (—N—C═O), thiocyanate groups (—S—CN), isothiocyanate groups (—N═C═S), nitrosamine groups (═N—N═O), thionitrosamine groups (═N—N═S), nitramine groups (═N—NO2), thionitramine groups (═N—NS2), carbonylnitrene groups (—CO—N), thiocarbonylnitrene groups (—CS—N), sulfenyl halides (—S—X), sulfoxides (—S═O), sulfones (═S[═O]2), sulfinyl groups (—N═S═O), thiosulfinyl groups (—N═S=S), sulfenyl thiocyanato groups (—S—S—CN), sulfenyl cyanato groups (—S—O—CN), sulfodiimine groups (═S[═NH]2), sulfur dihaloimido groups (—N═SX2), sulfur oxide dihaloimido groups (—N═S[═O]X2), aminosulfur oxide trihalide groups (═N—S[═O]X3), sulfonyl azide groups (—S[═O]2N3), sulfonyl thiocyanate groups (—S[═O]2SCN), sulfonyl cyanate groups (—S[═O]2OCN), sulfonyl cyanide groups (—S [═O]2CN), halosulfonate groups (—S[═O]2OX), phosphonyl thiocyanate groups (—P[═O]OHSCN), phosphonyl cyanate groups (—P[═O]OHOCN), and phosphonyl cyanide groups (—P[═O]OHCN). In this way, the characteristics of less typical coordinating ligands may be adjusted so that the resultant MnIII- or MnIV-valence stabilizer compound does exhibit some degree of corrosion inhibition. Conversely, the physical characteristics of typical coordination compounds can be adjusted so that they are no longer suitable as a corrosion inhibitor.
[0090] Valence stabilizers can be either organic or inorganic compounds. Manganese coordination chemistry, which has been the subject of numerous scientific studies for almost 100 years, identifies chemical binding preferences, structure stability, and the physical properties of the resulting compounds. Producing effective MnIII- and/or MnIV-valence stabilizer compounds requires understanding the electrostatic and structural influence of candidate species on the compound. The solubility of the valence stabilized MnIII- and/or MnIV-compound scales roughly with the inverse of its diameter. The MnIII and MnIV ions and their layer of negatively charged hydroxyl ions are very small, which results in a high degree of aqueous solubility. The field strength of the complex also scales with the inverse of its physical diameter. Large compounds with an optimal degree of solubility will not necessarily be ideal with respect to the size of their electrostatic double layer. The size of the ligand must therefore be balanced against the desired electrical properties. The MnIII ion generally favors complexation either in the square pyramidal (coordination number 5) or octahedral (coordination number 6) arrangements, although it will occasionally be found in a pentagonal bipyramid arrangement. The MnIV ion almost exclusively favors complexation in the octahedral (coordination number 6) arrangement. Valence stabilizers (and stabilizer combinations) should be selected with the goal of achieving these coordinations.
[0091] Stabilizers can be designed that result in manganese compounds with the necessary physical, electrical, and chemical properties to perform as corrosion inhibitors with this information. The nature of a particular valence stabilizer shell surrounding the manganese ion, or combination of valence stabilizers, can be further manipulated by the selection of appropriate “shaping groups” and heteroatoms at the binding site. Inorganic valence stabilizers are typically oxygen-containing coordinations. Therefore, manipulation of different sized ionic complexes around the MnIII or MnIV ions is best controlled through adjustment of the heteroatoms (e.g., Mo, W, Te, etc.) within these “polymerized” oxygen-containing ionic complexes (ligands).
[0092] For organic compounds, the physical geometry of the binding sites is important to the stability of the MnIII- or MnIV-stabilizer compound. The influence of site geometry becomes evident when the solvation shell of a MnIII or MnIV ion is replaced by the ligand donor atoms as when pigments are formed. The number of available ligand binding sites should be at least equal to the standard coordination number of the MnIII or MnIV ion. The balance between solvation of the ligand and MnIII and/or MnIV and their complexation where MnIII or MnIV is solvated by a specific ligand is critical in maintaining stability. MnIII- or MnIV-ligand attraction increases with the number of available binding sites on the ligand. However, with an increasing number of binding sites, site-site repulsions will also increase, resulting in lower stability.
[0093] The number of binding sites available on the complexing ligand is important to the resulting MnIII- or MnIV-stabilizer's properties. Several ligands are required to effectively stabilize MnIII or MnIV if the chosen ligand has only one binding site. For example, six NH3 ligands are needed to octahedrally coordinate MnIII in a hexaaminemanganese(III) compound because NH3 has only one binding site. Bulky ligands with only one binding site, like pyridine, can be sterically hindered from packing tightly around the ion and will result in decreased compound stability. Conversely, macrocyclic organic and polymeric inorganic ligands can have many suitable binding sites. However, instability will result if a MnIII or MnIV ion is not completely embraced by all of the multiple macromolecular bonding sites on the ligand. For example, if a macromolecule surrounding the MnIII or MnIV ion has an insufficient number of binding sites available for charge balance, then the MnIII- or MnIV-stabilizer compound will be much less stable than a macromolecule that contains an adequate number of sites.
[0094] The stability of the MnIII- or MnIV-organic compound is strongly influenced by the charge, charge sign, and degree of polarizability of specific binding sites. Factors influencing compound stability include: 1) ion-pair interactions for charged ligands and MnIII or MnIV; 2) ion-dipole and ion-induced dipole interactions for neutral ligands; 3) hydrogen bonding; and 4) the hard-soft acid-base (HSAB) rules convention of coordination chemistry. HSAB rules help identify functional groups on ligands that might be effective as binding sites. Optimum binding for organic valence stabilizers to MnIII or MnIV will be with ligands with hard bonding species such as those that contain oxygen or nitrogen. Certain coordination complexes of the soft base sulfur are also effective for binding with MnIII or MnIV. HSAB rules can also help identify groups that might provide a degree of polarization to the stabilizer because of their large dipole moments. The nature-of bonding-between the MnIII or MnIV ion/oxide cluster and the stabilizer ligand can be altered by using a substituent group to modify the stabilizer. Specific interactions between the ligand and MnIII or MnIV can be tailored by substituent group selection coupled with altering the size or geometry of the complexing ligand. Some substituent groups, such as carbonyls (ketones, amides, ureas), nitro groups, cyano groups, and azido groups have large dipole moments. The polarization of the MnIII- or MnIV-stabilizer can therefore be optimized via evaluation of the effect of ligand type and substituents.
[0095] Finally, the size of the valence stabilizer plays an important role in solubility control of the resultant MnIII- or MnIV-valence stabilizer compound. As the ligand increases in size, it becomes more difficult to keep it in solution, therefore lowering the solubility. However, this must be balanced against the fact that as ligands are increased in size, it also becomes more difficult to establish the necessary dipoles at the compound/water interface. The size of the ligand must therefore be balanced against the desired electrical properties. The addition (or subtraction) of functional groups on organic valence stabilizers can be used to modify the solubility of the formed Mn+3 or Mn+4/valence stabilizer species. For example, the addition of sulfonated groups (—SO3−) to organic valence stabilizers will significantly increase the solubility in water. Other substituent groups that will increase the solubility in water include: carboxyl groups (—CO2—), hydroxyl groups (—OH), ester groups (—CO3—), carbonyl groups (═C═O), amine groups (—NH2), nitrosamine groups (═N—N═O), carbonylnitrene groups (—CO—N), sulfoxide groups (═S═O), sulfone groups (═S[═O]2), sulfinyl groups (—N═S═O), sulfodiimines (═S[═NH]2), sulfonyl halide groups (—S[═O]2X), sulfonamide groups (—S[═O]2NH2), monohalosulfonamide groups (—S[═O]2NHX), dihalosulfonamide groups (—S[═O]2MX2), halosulfonate groups (—S[═O]2OX), halosulfonate amide groups (═N—S[═O]2X), aminosulfonate groups (═N—S[═O]2OH), iminodisulfonate groups (—N[SO3−]2), phosphonate groups (—PO3−2), phospbonamide groups (—PO2NH2−), phosphondiamide groups (—PO[NH2]2), aminophosphonate groups (—N—PO3−2), and iminodiphosphonate groups (—N[PO3−2]2). Conversely, the addition of nitro groups (—NO2), perfluoroalkyl groups (—CxF2x+1), perchloroalkyl groups (—CxCl2x+1), nitramine groups (—N—NO2), thioketone groups (═C═S), sulfenyl halide groups (—S—X), and sulfur dibaloimide groups (—N═SX2) to organic valence stabilizers will decrease the solubility in water. In this way, the solubility characteristics of valence stabilizers can be “tailored” to meet specific binder/resin needs.
[0096] Valence stabilizers-and combinations of stabilizers can be manipulated by the selection of “shaping groups” and heteroatoms positioned at the binding site. Saturated organic chains can form flexible ligands that wrap around MnIII- or MnIV- and can enhance their stability. Unsaturated organics typically have less freedom to bend and contort and are less likely to be a ligand that can wrap or fit around the MnIII or MnIV ions. Addition of substituents onto an organic ligand may further restrict its freedom to flex. For example, the attachment of a phenyl group onto an organic valence stabilizer that contains two or more binding sites will likely restrict the ability of that ligand to flex around the MnIII or MnIV ions so as to coordinate it as a square pyramid or octahedral complex.
[0097] The physical, chemical, and electrostatic requirements for the design of effective pigments based on MnIII- or MnIV-stabilizer compounds result in lists of stabilizers that may be divided into wide band or narrow band stabilizer classes for MnIII or MnIV, depending upon the application. Wide band valence stabilizers can be used under a wide variety of service conditions (e.g., corroding specie, temperature, etc.) to achieve a high degree of corrosion resistance. Wide band physical properties (stability, solubility, and polarization) can be achieved by both inorganic or organic valence stabilizers. The desirable physical property of ion exchange can also be achieved with both inorganic and organic coordination compounds. “Narrow band” valence stabilizers result in satisfactory pigments only under limited applications. Table 3 lists the wide and narrow band valence stabilizers for MnIII and MnIV depending upon the specific application.
[0098] The compounds listed here are general guides for the initial selection of a coordination compound and do not represent a complete list. Tailoring substituent groups and the selection of cations or anions for charge balance can influence whether a particular MnIII- or MnIV-stabilizer compound will have wide band or narrow band corrosion inhibiting characteristics. Both inorganic or organic valence stabilizers may form compounds with the necessary physical properties of stability, solubility, and polarization to be effective corrosion inhibiting pigments. 4 TABLE 3 Wide and Narrow Band Valence Stabilizers for Trivalent and/or Tetravalent Manganese Replacements for Hexavalent Chromium or Tetravalent Lead Pigments Hexavalent Chromium Wide Narrow or Tetravalent Lead Band Valence Band Valence Pigment to be Replaced Stabilizers Stabilizers Zinc Chromates Inorganic: Inorganic: (including basic forms) Molybdates, tungstates, Bismuthates, Strontium Chromates vanadates, niobates, germanates, Calcium Plumbate tantalates, tellurates, arsenates periodates, iodates, antimonates, stannates, sulfates, polyphosphates Organic: Organic: See Table 4 See Table 5 Lead Chromates Inorganic: Inorganic: (including basic forms) Oxygen, titanates, Carbonates Lead Molybdate-Chromate zirconates, tantalates, Lead Silicochromate aluminates, silicates, phosphates, borates Organic: Organic: none none Red Lead Inorganic: Inorganic: Oxygen, titanates, None zirconates, tantalates, aluminates, silicates Organic: Organic: none none
[0099] 3a) Wide Band Inorganic Valence Stabilizers
[0100] Wide band inorganic valence stabilizers are formed around the MnIII or MnIV ion by “polymerizing” in synthesis solution. Inorganic wide band valence stabilizers for MnIII or MnIV for “sparingly soluble” pigments include molybdates (Mo+6, Mo+5, or Mo+4, for example [Mn+4Mo9O32]6− and [Mn+4Mo12O40]4−), tungstates (W+6, W+5, or W+4, for example [Mn+4W12O40]4− and [Mn+32W22O74]10−), vanadates (V+5 and V+4, for example [Mn+4V13O38]7− and [Mn+4V11O32]5−), niobates (Nb+5 and Nb+4, for example [Mn+4Nb12O38]12−), tantalates (Ta+5 and Ta+4, for example [Mn+4Ta12O38]12−), tellurates (Te+6 and Te+4, for example [Mn+4Te3O18]14−), periodates (1+7, for example [Mn+4I3O18]11−), iodates (1+5, for example [Mn+4I6O18]2−), antimonates (Sb+5 and Sb+3), stannates (Sn+4), sulfates (S+6, such as manganese spinels [Mn+3(SO4)2]1−), and polyphosphates (P+5, for example [Mn+3P3O10]2− and [Mn+3P2O7]1−). Many of these inorganics form octahedral and square pyramidal heteropolymetallate structures on precipitation from solution. For example, tellurate ions begin to polymerize near pH 5 in water and will complex with MnIII or MnIV ions in basic solution pH's. Therefore, as the pH is raised in the pigment synthesis bath, the tellurate ion polymerizes to polymorphs, which then complex the MnII or MnIV ion.
[0101] The general structural aspects of heteropolymetallates are well understood, and the stability of heteropolymetallates as a function of composition and structure is also well-characterized. The relatively unstable MnIII or MnIV ions are protected and stabilized within the surrounding octahedral and square pyramidal groups, although specific configurations of the heteropolymetallate anions differ from stabilizer to stabilizer (i.e., from molybdate to periodate or iodate). The dimensions of the octahedra and square pyramids are controlled by the size of the heteroatom (e.g., Mo, W, or Te) around which they are assembled.
[0102] A MnIII or MnIV ion trapped by the precipitation of these heteropolymetallates and its resulting “ion within a cage” structure can exhibit an even greater apparent volume due to the development of a large electrostatic double layer. This will influence both the valence stabilization of the MnIII or MnIV, as well as the solubility of the assembled compound. These compounds are reported to be excellent ion exchange agents for alkali ions. This caging structure serves to lower the solubility of the MnIII or MnIV because the chemical elements typically associated with these valence stabilizers (e.g., I, Te, Mo, or W) are all inherently less soluble in water than Mn. These materials can also establish oriented dipoles with the interior MnII or MnIV ion and form an electrostatic double layer during aqueous corrosion. Finally, the elements associated with these valence stabilizers themselves can contain high valence ions (i.e., V+5, Te+6, or Mo+6), which will also serve somewhat in corrosion protection, although not to the degree of MnIII or MnIV (or CrVI), due to their lower redox potential.
[0103] Water-soluble precursors for these materials are generally used so that the synthesis can be carried out from aqueous solution. Many elements associated with these stabilizers (e.g., Mo, W, or Te) do not typically form water-soluble compounds so the identification of suitable precursors can be difficult.
[0104] Complex, partially-polymerized salts such as para- or meta-polymorphs for each compound may also be used as precursors. These polymorphs typically exhibit slightly lower solubilities in water than the simple salts. Peroxo-salts of these compounds, especially permolybdates, pertungstates, and pervanadates may also be used as precursors. Formation of the chosen heteropolymetallates from precursors such-as the fluorides, chlorides, bromides, nitrates, and perchlorates (e.g., SnCl4 to form heterostannates and SbF5 to form heteroantimonates) can be difficult, but may be acceptable in certain circumstances. A valence stabilizer can be a cross between two or more of the wide-band inorganic valence stabilizers listed above. For example, a valence stabilizer composed of a periodate and a molybdate may be desirable in some situations. During the synthesis process, both of these materials will polymerize to form a mixed periodate/molybdate valence stabilizer out of the pigment solution.
[0105] The most notable valence stabilizer for low and insoluble MnIII and MnIV pigments is oxygen (O), as evidenced by the natural stability of such compounds as MnO2, Mn3O4, Mn2O3 and MnOOH, all of which contain MnIII and/or MnIV ions. In instances where oxygen is used as a valence stabilizer for MnIII or MnIV, differences in addendum cations (i.e., Ca+2 in CaMn2O4 or Zn+2 in ZnMn2O4) are observed to alter the solubility of the formed compound, and its performance as a corrosion inhibitor in a given binder system. This is discussed under Section 4 describing Additional Solubility Control Agents.
[0106] Additional wide band valence stabilizers for MnIII or MnIV for “low solubility” or “insoluble” pigments include silicates (Si+4, for example [Mn+3Si2O6]1−), borates (B+3, for example Mn+32B4O9), phosphates (P+5, for example Mn+3PO4), titanates (Ti+4), zirconates (Zr+4), and aluminates (Al+3). These compounds can also form octahedral or square pyramids, but have a higher tendency to form chain-like structures during calcining or firing. Combinations of these materials, such as phosphosilicates, aluminosilicates, or borosilicates may also function as wide band valence stabilizers for low and insoluble MnIII and MnIV compounds.
[0107] 3b) Wide Band Organic Valence Stabilizers
[0108] A variety of organic compounds meet the criteria to be typical wide band valence stabilizers for MnIII or MnIV. These coordination ligands produce MnIII or MnIV valence stabilized compounds that fulfill the general requirements of a MnIII or MnIV pigment material. Organic compounds can be very effective manganese stabilizers and provide the greatest degree of freedom in designing new manganese-stabilizer compounds with new functionalities. More possible organic valence stabilizer species exist than inorganic valence stabilizers because of the immense number of organic compounds and functionalities from which to choose. Water-soluble precursors for the organic valence stabilizers are generally used so that pigment synthesis can be carried out in aqueous solution. However, alcohol or hydrocarbon soluble species can also be used.
[0109] The number of wide band (and narrow band) organic compounds that are acceptable as valence stabilizers for trivalent or tetravalent manganese is limited. Common organic compounds such as alcohols, aldehydes, ketones, esters, ethers, alkyl or aromatic halides, most carboxylic acids, anhydrides, phenols, sulfonic acids, phosphonic acids, carbohydrates, waxes, fats, sugars, and oils are not as effective as the structural types described in these Tables to stabilize the trivalent or tetravalent manganese ion. At best, some of the organic types described in these Tables may presently be used for other industrial applications, but their incorporation into corrosion-inhibiting blends to stabilize trivalent or tetravalent manganese has heretofore been unrecognized.
[0110] The choice of substituent functional groups on these general classes of valence stabilizers will affect the physicochemical properties of the MnIII- or MnIV-containing compound and the corrosion resistance achieved using that compound. For example, the addition of —NH2 or ═O substituents increases the net polarization of the overall net MnIII or MnIV/valence stabilizer compound, but will also increase its water solubility. Careful molecular design of MnIII and MnIV compounds is necessary in order to achieve desired performance characteristics.
[0111] In general, the bonding atoms in typical organic valence stabilizers are nitrogen, oxygen, or sulfur. Bonding atoms such as phosphorus, carbon, silicon, tin, arsenic, and antimony are much less desirable due to problems with valence stability, toxicity, or solubility. Other stable coordinations (like pentagonal bipyramidal) are known, even though these particular agents prefer octahedral or square pyramidal coordination with Mn+3 or Mn+4. These valence stabilizers all serve to stabilize the Mn+3 or Mn+4 ions within a sparingly soluble complex that can exhibit a polar character in aqueous solution. 5 TABLE 4 Wide Band Organic Valence Stabilizers for the Mn+3 and Mn+4 Ions General Structural Name (Type of Organic) Structural Representation N Valence Stabilizer #1: NH3, NH2R, NHR2, and NR3 where R Monoamines represents H or any organic functional group (N Monodentates) wherein the number of carbon atoms ranges from 0 to 40, optionally having halogen or polarizing or water-insolubilizing/ solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #2: R′—N—R—N—R″, where R, R′, and R″ Diamines represent H or any organic functional group (N—N Bidentates) wherein the number of carbon atoms ranges from 0 to 40, optionally having halogen or polarizing or water-insolubilizing/ solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #3: R—N—R′—N—R″—N—R′′′, where R, R′, Triamines (either N—N R″, and R′′′ represent H or any organic Bidentates or N—N functional group wherein the number of carbon Tridentates) atoms ranges from 0 to 40, optionally having halogen or polarizing or water-insolubilizing/ solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #4: R—N—R′—N—R″—N—R″′—N—R″″, Tetramines (N—N where R, R′, R″, R″′, and R″″ represent H or Bidentates, N—N any organic functional group wherein the Tridentates, or N—N number of carbon atoms ranges from 0 to 40, Tetradentates) optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #5: R—N—R′—N—R″—N—R″′—N—R″″— Pentamines (N—N N—R″″′, where R, R′, R″, R″′, R″″, and Bidentates, N—N R″″′ represent H or any organic functional Tridentates, or N—N group wherein the number of carbon atoms Tetradentates) ranges from 0 to 40, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #6: R—N—R′—N—R″—N—R″′—N—R″″— Hexamines (N—N N—R″″′—N—R″″″, where R, R′, R″, R″′, Bidentates, N—N R″″, R″″′, and R″″″ represent H or any Tridentates, N—N organic functional group wherein the number Tetradentates, or N—N of carbon atoms ranges from 0 to 40, Hexadentates) optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #7: Five membered heterocyclic ring containing Five-Membered Heterocyclic one, two, three, or four nitrogen atoms, all of Rings containing One, which may or may not function as binding Two, Three, or Four sites. Can include other ring systems bound Nitrogen Atoms wherein at to this heterocyclic ring, but they do not least one Nitrogen Atom is coordinate with the stabilized, high valence a Binding Site (N metal ion. Ring can also contain O, S, or P Monodentates or N—N atoms. This 5-membered ring and/or Bidentates) attached, uncoordinating rings may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. N Valence Stabilizer #8: Six membered heterocyclic ring containing Six-Membered Heterocyclic one, two, three, or four nitrogen atoms, all Rings containing One, of which may or may not function as binding Two, Three, or Four sites. Can include other ring systems bound Nitrogen Atoms wherein at to this heterocyclic ring, but they do not least one Nitrogen Atom is coordinate with the stabilized, high valence a Binding Site (N metal ion. Ring can also contain O, S, or Monodentates or N—N P atoms. This 6-membered ring and/or Bidentates) attached, uncoordinating rings may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. N Valence Stabilizer #9: Five membered heterocyclic ring(s) Five-Membered Heterocyclic containing one, two, three, or four nitrogen Rings containing One, atoms. In addition, ligand contains additional Two, Three, or Four nitrogen-containing substituents (usually Nitrogen Atoms and having amines) that constitute N binding sites. Can at least one additional include other ring systems bound to the Nitrogen Atom Binding heterocyclic ring or to the N-containing Site not in a Ring (N substituent, but they do not coordinate with Monodentates, N—N the stabilized, high valence metal ion. Bidentates, N Ring(s) can also contain O, S, or P atoms. Tridentates, N—N This 5-membered ring(s) and/or attached, Tetradentates, or uncoordinating rings and/or N containing N—N Hexadentates) substituent(s) may or may not have halogen or polarizing or water-insolubilizing/ solubilizing groups attached. N Valence Stabilizer #10: Six membered heterocyclic ring(s) Six-Membered Heterocyclic containing one, two, three, or four nitrogen Rings containing One, atoms. In addition, ligand contains additional Two, Three, or Four nitrogen-containing substituents (usually Nitrogen Atoms at least one amines) that constitute N binding sites. Can additional Nitrogen Atom include other ring systems bound to the Binding Site not in a Ring heterocyclic ring or to the N-containing (N Monodentates, N—N substituent, but they do not coordinate with Tridentates, N—N the stabilized, high valence metal ion. Tetradentates, or N—N Ring(s) can also contain O, S, or P atoms. Bidentates, N—N This 6-membered ring(s) and/or attached, Hexadentates) uncoordinating rings and/or N-containing substituent(s) may or may not have halogen or polarizing or water-insolubilizing/ solubilizing groups attached. N Valence Stabilizer #11:. Five membered heterocyclic ring(s) Five-Membered Heterocyclic containing one, two, three, or four nitrogen Rings containing One, atoms. In addition, ligand contains additional Two, Three, or Four nitrogen-containing rings that constitute N Nitrogen Atoms at least binding sites. Can include other ring systems one additional Nitrogen bound to the N-containing heterocyclic rings, Atom Binding Site in a but they do not coordinate with the Separate Ring (N stabilized, high valence metal ion. Ring(s) Monodentates, N—N can also contain O, S, or P atoms. This Bidentates, N—N 5-membered ring(s) and/or additional N- Tridentates, N—N containing ring(s) and/or attached, Tetradentates) uncoordinating rings may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. N Valence Stabilizer #12: Six membered heterocyclic ring(s) Six-Membered Heterocyclic containing one, two, three, or four nitrogen Rings containing One, atoms. In addition, ligand contains additional Two, Three, or Four nitrogen-containing rings that constitute N Nitrogen Atoms at least one binding sites. Can include other ring systems additional Nitrogen Atom bound to the N-containing heterocyclic Binding Site in a Separate rings, but they do not coordinate with the Ring (N Monodentates, stabilized, high valence metal ion. Ring(s) N—N Bidentates, N—N can also contain O, S, or P atoms. This Tridentates, N—N 6-membered ring(s) and/or additional N- Tetradentates) containing ring(s) and/or attached, uncoordinating rings may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. N Valence Stabilizer #13: Macrocyclic ligands containing two, three, Two-, Three-, Four-, Six-, four, six, eight, or ten nitrogen binding sites Eight-, and Ten- Membered to valence stabilize the central metal ion. Macrocyclics, Can include other hydrocarbon or ring Macrobicyclics, and systems bound to this macrocyclic ligand, Macropolycyclies but they do not coordinate with the (including Catapinands, stabilized, high valence metal ion. This Cryptands, Cyclidenes, and ligand and/or attached, uncoordinating hydrocarbons/rings may or may Sepulchrates) wherein all not have halogen or polarizing or water- Binding Sites are composed insolubilizing/solubilizing groups attached. of Nitrogen (usually amine or imine groups) and are not contained in Component Heterocyclic Rings (N—N Bidentates, N—N Tridentates, N—N Tetradentates, and N—N Hexadentates) N Valence Stabilizer #14: Macrocyclic ligands containing a total of Four-, Six-, Eight-, or four, six, eight, or ten five-membered Ten-Membered Macro- heterocyclic rings containing nitrogen cyclics, Macrobicyclics, binding sites. Can include other and Macropolycyclics hydrocarbon/ring systems bound to this (including Catapinands, macrocyclic ligand, but they do not Cryptands, Cyclidenes, and coordinate with the stabilized, high valence Sepulchrates) wherein all metal ion. This ligand and/or attached, Binding Sites are composed uncoordinating hydrocarbon/rings may or of Nitrogen and are may not have halogen or polarizing or contained in Component water-insolubilizing groups attached. 5-Membered Heterocyclic Rings (N—N Bidentates, N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) N Valence Stabilizer #15: Macrocyclic ligands containing at least one Four-, Six-, Eight-, or Ten- 5-membered heterocyclic ring. These Membered Macrocyclics, heterocyclic rings provide nitrogen binding Macrobicyclics, and sites to valence stabilize the central metal Macropolycyclics ion. Other amine or imine binding sites can (including Catapinands, also be included in the macrocyclic ligand, Cryptands, Cyclidenes, so long as the total number of binding sites and Sepulchrates) is four, six, eight, or ten. Can include other wherein all Binding Sites hydrocarbon/ring systems bound to this are composed of Nitrogen macrocyclic ligand, but they do not and are contained in a coordinate with the stabilized, high valence Combination of 5- metal ion. This ligand and/or attached, Membered Heterocyclic uncoordinating hydrocarbon/rings may or may Rings and Amine or Imine not have halogen or polarizing or water- Groups (N—N Bidentates, insolubilizing groups attached. N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) N Valence Stabilizer #16: Macrocyclic ligands containing a total of Four-, Six-, Eight-, or Ten- four, six, eight, or ten six-membered Membered Macrocyclics, heterocyclic rings containing nitrogen Macrobicyclics, and binding sites. Can include other Macropolycyclics hydrocarbon/ring systems bound to this (including Catapinands, macrocyclic ligand, but they do not Cryptands, Cyclidenes, and coordinate with the stabilized, high valence Sepulchrates) wherein all metal ion. This ligand and/or attached, Binding Sites are composed uncoordinating hydrocarbon/rings may or of Nitrogen and are may not have halogen or polarizing or water- contained in Component insolubilizing groups attached. 6-Membered Heterocyclic Rings (N—N Bidentates, N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) N Valence Stabilizer #17: Macrocyclic ligands containing at least one Four-, Six-, Eight-, or Ten- 6-membered heterocyclic ring. These Membered Macrocyclics, heterocyclic rings provide nitrogen binding Macrobicyclics, and sites to valence stabilize the central metal Macropolycyclics ion. Other amine or imine binding sites can (including Catapinands, also be included in the macrocyclic ligand, Cryptands, Cyclidenes, so long as the total number of binding and Sepulchrates) sites is four, six, eight, or ten. Can include wherein all Binding Sites other hydrocarbon/ring systems bound to are composed of Nitrogen this macrocyclic ligand, but they do not and are contained in a coordinate with the stabilized, high valence Combination of 6- metal ion. This ligand and/or attached, Membered Heterocyclic uncoordinating hydrocarbon/rings may or Rings and Amine or Imine may not have halogen or polarizing or water- Groups (N—N Bidentates, insolubilizing groups attached. N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) N Valence Stabilizer #18: R′—NH—C(—R)═N—R″, where R, R′, Amidines and Diamidines and R″represent H or any organic functional (N—N Bidentates and group wherein the number of carbon atoms N—N Tetradentates) ranges from 0 to 40, optionally having halogen or polarizing or water-insolubilizing/ solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #19: RR′—N—C(═NH)—NR″—C(═NH)— Biguanides NR″′R″″ for biguanides, RR′—N— (Imidodicarbonimidic C(═NH)—NR″—NH—C(═NH)—NR″′R″″ Diamides or Dihydrazides), for biguanidines, where R, R′, R″, R″′, and Biguanidines, R″″ represent H, NH2, or any organic Imidotricarbonimidic functional group wherein the number of Diamides or Dihydrazides, carbon atoms ranges from 0 to 40, halogen Imidotetracarbonimidic or polarizing or water-insolubilizing/ Diamides or Dihydrazides, solubilizing groups attached. Ligand can also Dibiguanides, contain nonbinding N, O, S, or P atoms. Bis(biguanidines), Polybiguanides, and Poly(biguanidines) (N—N Bidentates, N—N Tridentates, N—N Tetradentates, and N—N Hexadentates) N Valence Stabilizer #20: RR′—N—C(═NH)—CR″R′″—C(═NH)— Diamidinomethanes, NR″″R″″′, where R, R′, R″, R″′, R″″, and Bis(amidinomethanes), and R″″′ represent H, NH2, or any organic Poly(amidinomethanes) functional group wherein the number of (N—N Bidentates, N—N carbon atoms ranges from 0 to 40, optionally Tridentates, N—N having halogen or polarizing or water- Tetradentates, and insolubilizing/solubilizing groups attached. N—N Hexadentates) Ligand can also contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #21: RR′—N—C(═NH)—NR″—C(═NH)—R″′ Imidoylguanidines, for imidoylguanidines, and RR′—N— Amidinoguanidines, C(═NH)—NR″—NH—C(NH)—R″′ for Bis(imidoylguanidines), amidinoguanidines, where R, R′, R″, and Bis(amidinoguanidines), R″′ represent H, NH2, or any organic Poly(imidoylguanidines), functional group wherein the number of and Poly(amidino- carbon atoms ranges from 0 to 40, optionally guanidines) (N—N having halogen or polarizing or water- Bidentates, N—N insolubilizing/solubilizing groups attached. Tridentates, N—N Ligand can also contain nonbinding N, O, S, Tetradentates) or P atoms. N Valence Stabilizer #22: RR′—N—C(NH)—O—C(═NH)-NR″R″′, Diformamidine oxides where R, R′, R″, and R″′ represent H, NH2, (Dicarbonimidic Diamides or any organic functional group wherein the or Dihydrazides), number of carbon atoms ranges from 0 to 40, Tricarbonimidic Diamides optionally having halogen or polarizing or or Dihydrazides, water-insolubilizing/solubilizing groups Tetracarbonimidic attached. Ligand can also contain nonbinding Diamides or Dihydrazides, N, O, S, or P atoms. Bis(diformamidine oxides), and Poly(diformamidine oxides) (N—N Bidentates, N—N Tridentates, N—N Tetradentates) N Valence Stabilizer #23: RR′—N—C(═NH)—S—C(═NH)— Diformamidine Sulfides NR″R″′, where R, R′, R″, and R″′ represent (Thiodicarbonimidic H, NH2, or any organic functional group Diamides or Dihydrazides), wherein the number of carbon atoms ranges Thiotricarbonimidic from 0 to 40, optionally having halogen or Diamides or Dihydrazides, polarizing or water-insolubilizing/ Thiotetracarbonimidic solubilizing groups attached. Ligand can also Diamides or Dihydrazides, contain nonbinding N, O, S, or P atoms. Bis(diformamidine sulfides), and Poly(diformamidine sulfides) (N—N Bidentates, N—N Tridentates, N—N Tetradentates) N Valence Stabilizer #24: R—O—C(═NH)—NR′—C(═NH)—O—R′ Imidodicarbonimidie Acids, for imidodicarbomimidic acids, and R—O— Diimidodicarbonimidic C(═NH)—NR′—NH—C(═NH)—O—R″ Acids, Imidotricarbon- for diimidodicarbonimidic acids, where R, imidic Acids, Imidotetra- R′, and R″ represent H, NH2, or any organic carbonimidic Acids, and functional group wherein the number of derivatives thereof (N—N carbon atoms ranges from 0 to 40, optionally Bidentates, N—N having halogen or polarizing or water- Tridentates, N—N insolubilizing/solubilizing groups attached. Tetradentates, and Ligand can also contain nonbinding N, O, S, N—N Hexadentates) or P atoms. N Valence Stabilizer #25: R—S—C(═NH)—NR′—C(═NH)—S—R″ Thioimidodicarbonimidic for thioimidodicarbonimidic acids, and R— Acids, Thiodiimidodi- S—C(═NH)—NR′—NH—C(═NH)—S carbonimidic Acids, —R″ for thiodiimidodicarbonimidic acids, Thioimidotricarbonimidic where R, R′, and R″ represent H, NH2, or Acids, Thioimidotetra- any organic functional group wherein the carbonimidic Acids, and number of carbon atoms ranges from 0 to 40, derivatives thereof optionally having halogen or polarizing or (N—N Bidentates, N—N water-insolubilizing/solubilizing groups Tridentates, N—N attached. Ligand can also contain nonbinding Tetradentates, and N, O, S, or P atoms. N—N Hexadentates) N Valence Stabilizer #26: R—C(═NH)—NR′—C(═NH)—R″ for Diimidoylimines, diimidoylimines, and R—C(═NH)—NR′— Diimidoylhydrazides, NH—C(═NH)—R″ for diimidoyl- Bis(diimidoylimines), hydrazides, where R, R′, and R″ represent Bis(diimidoylhydrazides), H, NH2, or any organic functional group Poly(diimidoylimines), and wherein the number of carbon atoms ranges Poly(diimidoylhydrazides) from 0 to 40, optionally having halogen or (N—N Tridentates and polarizing or water-insolubilizing/ N—N Hexadentates) solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #27: RR′—N—S(═NH)(═O)—OR″ or RR′— Imidosulfamides, N—S(═NH)(═O)—N—R″R″′ for Diimidosulfamides, imidosulfamides, and RR′—N— Bis(imidosulfamides), S(═NH)(═NH)—OR″ or RR′—N— Bis(diimidosulfamides), S(═NH)(═NH)—N—R″R″′ for diimido- Poly(imidosulfamides), and sulfamides, where R, R′, R″, and R″′ Poly(diimidosulfamides) represent H, NH2, or any organic functional (N—N Bidentates, N—N group wherein the number of carbon atoms Tridentates, N—N ranges from 0 to 40, optionally having Tetradentates, and halogen or polarizing or water-insolubilizing/ N—N Hexadentates) solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #28: (NH═)P(—NRR′)(—NR″R″′)(—NR″″R″″′), Phosphoramidimidic where R, R′, R″, R″′, R″″, and R″″′ represent Triamides, Bis(phosphor- H, NH2, or any organic functional group amidimidic triamides), and wherein the number of carbon atoms ranges Poly(phosphoramidimidic from 0 to 40, optionally having halogen or triamides) and derivatives polarizing or water-insolubilizing/ thereof (N—N Bidentates, solubilizing groups attached. Ligand can also N—N Tridentates, N—N contain nonbinding N, O, S, or P atoms. Tetradentates, and N—N Hexadentates) N Valence Stabilizer #29: (NH═)P(—NRR′)(OH)2 for phosphor- Phosphoramidimidic Acid, amidimidic acid, and (NH═)P(—NRR′) Phosphorodiamidimidic (—NR″R″′)(OH) for phosphorodiamidimidic Acid, Bis(Phosphor- acid, where R, R′, R″, and R″′ represent H, amidimidic Acid), NH2, or any organic functional group Bis(Phosphorodiamidimidic wherein the number of carbon atoms ranges Acid), Poly(Phosphor- from 0 to 40, optionally having halogen or amidimidic Acid), and polarizing or water-insolubilizing/ Poly(Phosphorodi- solubilizing groups attached. Ligand can also amidimidic Acid), contain nonbinding N, O, S, or P atoms. derivatives thereof (N—N Bidentates, N—N Tridentates, N—N Tetradentates, and N—N Hexadentates) N Valence Stabilizer #30: (NH═)P(—NRR′)(SH)2 for phos- Phosphoramidimidodithioic phoramidimidodithioic acid, and (NH═)P(— Acid, Phosphorodiamidi- NRR′)(—NR″R″′)(SH) for midothioic Acid, Bis(Phos- phosphorodiamidimidothioic acid, where R, phoramidimidodithioic R′, R″, and R″′ represent H, NH2, or any Acid), Bis(Phosphorodi- organic functional group wherein the number amidimidothioic Acid), of carbon atoms ranges from 0 to 40, Poly(Phosphoramidimido- optionally having halogen or polarizing or dithioic Acid), Poly(Phos- water-insolubilizing/solubilizing groups phorodiamidimidothioic attached. Ligand can also contain nonbinding Acid), and derivatives N, O, S, or P atoms. thereof (N—N Bidentates, N—N Tridentates, N—N Tetradentates, and N—N Hexadentates) N Valence Stabilizer #31: R—N═N—R′ for azo compounds, Azo compounds including R—N═—NH—R′ for triazenes, where triazenes with amino, R, and R′ represent H or any organic imino, oximo, diazeno, or functional group wherein the number of hydrazido substitution at carbon atoms ranges from 0 to 40, optionally the ortho- (for aryl) or having halogen or polarizing or water- alpha- or beta- (for alkyl) insolubilizing/solubilizing groups attached. positions, Bis[o-(H2N—) (Must include ortho-amino, imino, oximo, or alpha- or beta- diazeno, or hydrazido substituted aryl azo (H2N—)azo compounds], compounds, and alpha- or beta-amino, or Poly[o-(H2N—) or imino, oximo, diazeno, or hydrazido alkyl alpha- or beta-(H2N—)azo azo compounds.) Ligand can also contain compounds) (N—N nonbinding N, O, S, or P atoms. Bidentates, N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) N Valence Stabilizer #32: R—N═N—C(═NH)—NR′R″ for diazene- Diazeneformimidamides formimidamides, and R—N═N—CR′R″— (Diazeneamidines), C(═NH)—NR″′R″″ for diazeneacetimid- Diazeneacetimidamides amides, where R, R′, R″, R″′, and R″″ (Diazene-alpha-amidino- represent H, NH2, or any organic functional alkanes(alkenes)), Bis(di- group wherein the number of carbon atoms azeneformimidamides), ranges from 0 to 40, optionally having Bis(diazeneacetimid- halogen or polarizing or water-insolubilizing/ amides), Poly(diazene- solubilizing groups attached. Ligand can also formimidamides), and contain nonbinding N, O, S, or P atoms. Poly(diazeneacetimid- amides) (N—N Bidentates, N—N Tetradentates, and N—N Hexadentates) N Valence Stabilizer #33: R—N═N—C(═NH)—OR′ for diazene- Diazeneformimidic Acid, formimidic acid, and R—N═N—CR′R″— Diazeneacetimidic Acid, C(═NH)—OR″′ for diazeneacetimidic acid, Bis(diazeneformimidic where R, R′, R″, and R″′ represent H, NH2, acid), Bis(diazene- or any organic functional group wherein the acetimidic acid), number of carbon atoms ranges from 0 to 40, Poly(diazeneformimidic optionally having halogen or polarizing or acid), Poly(diazene- water-insolubilizing/solubilizing groups acetimidic acid), and attached. Ligand can also contain nonbinding Bidentates, N—N N, O, 5, or P atoms. Tetradentates, and N—N Hexadentates) N Valence Stabilizer #34: R—N═N—C(═NH)—SR′ for diazene- Diazeneformimidothioic formimidothioic acid, and R—NN— Acid, Diazeneacetimido- CR′R″—C(═NH)—SR″′ for diazene- thioic Acid, Bis(diazene- acetimidothioic acid, where R, R′, R″, and formimidothioic acid), R″′ represent H, NH2, or any organic Bis(diazeneacetimidothioic functional group wherein the number of acid), Poly(diazene- carbon atoms ranges from 0 to 40, optionally formimidothioic acid), having halogen or polarizing or water- Poly(diazeneacetimido- insolubilizing/solubilizing groups attached. thioic acid), and Ligand can also contain nonbinding N, O, S, derivatives thereof or P atoms. (N—N Bidentates, N—N Tetradentates, and N—N Hexadentates) N Valence Stabilizer #35: R—N═N—C(NH)—R′ or R—N═N— Imidoyldiazenes, CR′R″—C(═NH)—R″′, where R, R′, R″, Bis(imidoyldiazenes), and and R″′represent H, NH2, or any organic Poly(imidoyldiazenes), functional group wherein the number of (N—N Bidentates, carbon atoms ranges from 0 to 40, optionally N—N Tetradentates having halogen or polarizing or water- and N—N Hexadentates) insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #36: RR′—N—C(═NH)—N═N—C(═NH)— Diazenediformimidamides NR″R″′ for diazenediformimidamides, and (1,2-Diazenediamidines), RR′—N—C(═NH)—CR″R″′—N═N— Diazenediacetimidamides CR″″R″″′—C(═NH)—NR″″″R″″″′ (1,2-Diazene-di-alpha- for diazenediacetimidamides, where R, R′, amidinoalkanes(alkenes)), R″, R′″, R″″, R″″′, R″″″, and R″″″′ represent Bis(diazenediformimid- H, NH2, or any organic functional group amides), Bis(diazenedi- wherein the number of carbon atoms ranges acetimidamides), Poly(di- from 0 to 40, optionally having halogen or azenediformimidamides), polarizing or water-insolubilizing/ and Poly(diazenedi- solubilizing groups attached. Ligand can also acetimidamides) (N—N contain nonbinding N, O, S, or P atoms. Tridentates and N—N Hexadentates) N Valence Stabilizer #37: RO—C(═NH)—N═N—C(═NH)—OR′ Diazenediformimidic Acid, for diazenediformimidic acid, and RO— Diazenediacetimidic Acid, C(═NH)—CR′R″—N═N—CR″′R″″— Bis(diazenediformimidic C(═NH)—OR″″′ for diazenediacetimidic acid), Bis(diazenedi- acid, where R, R′, R″, R″′, R″″, and R″″′ acetimidic acid), represent H, NH2, or any organic functional Poly(diazenediformimidic group wherein the number of carbon atoms acid), and Poly(diazenedi- ranges from 0 to 40, optionally having acetimidic acid), and halogen or polarizing or water-insolubilizing/ derivatives thereof solubilizing groups attached. Ligand can also (N—N Tridentates contain nonbinding N, O, S, or P atoms. and N—N Hexadentates) N Valence Stabilizer #38: RS—C(═NH)—N═N—C(═NH)—SR′ for Diazenediformimidothioic diazenediformimidothioic acid, and RS— Acid, Diazenediacetimido- C(═NH)—CR′R″—N═N—CR″′R″″— thioic Acid, Bis(diazene- C(═NH)—SR″″′ for diazenediacetimi- diformimidothioic acid), dothioic acid, where R, R′, R″, R″′, R″″, and Bis(diazenediacetimido- R″″′ represent H, NH2, or any organic thioic acid), Poly(diazene- functional group wherein the number of diformimidothioic acid), carbon atoms ranges from 0 to 40, optionally and Poly(diazenedi- having halogen or polarizing or water- acetimidothioic acid), and insolubilizing/solubilizing groups attached. derivatives thereof Ligand can also contain nonbinding N, O, S, (N—N Tridentates and or P atoms. N—N Hexadentates) N Valence Stabilizer #39: R—C(═NH)—N═N—C(NH)—R″or Diimidoyldiazenes, R—C(═NH)—CR′R″—N═N—CR″′R″″— Bis(diimidoyldiazenes), C(═NH)—R″″′, where R, R′, R″, R″′, R″″, and Poly(diimidoyl- and R″″′ represent H, NH2, or any organic diazenes), (N—N functional group wherein the number of Tridentates and N—N carbon atoms ranges from 0 to 40, optionally Hexadentates) having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #40: R—N═N—CR′═N—NR″R″′, where R, R′, Ortho-amino (or R″, and R″′ represent H, or any organic -hydrazido) Substituted functional group wherein the number of Formazans, Bis(o-amino or carbon atoms ranges from 0 to 40, optionally -hydrazido substituted having halogen or polarizing or water- formazans), and Poly(o- insolubilizing/solubilizing groups attached. amino or -hydrazido (Must include ortho-amine or hydrazide substituted formazans) substituted aryl R derivatives, and beta- (N—N Bidentates, N—N amine or hydrazide substituted alkyl R Tridentates, N—N derivatives.) Ligand can also contain Tetradentates, and N—N nonbinding N, O, S, or P atoms. Hexadentates) N Valence Stabilizer #41: RR′C═N—N═CR″R″′ or RR′C═N— Ortho-amino (or NR″R″′ (for ketazines), where R, R′, R″, -hydrazido) Substituted and R″′ represent H, or any organic Azines (including functional group wherein the number of ketazines), Bis(o-amino carbon atoms ranges from 0 to 40, optionally or hydrazido substituted having halogen or polarizing or water- azines), and Poly(o-amino insolubilizing/solubilizing groups or hydrazido substituted attached. (Must include ortho-amine or azines) (N —N Bidentates, hydrazide substituted aryl R derivatives, and N—N Tridentates, beta-amine or hydrazide substituted alkyl R N—N Tetradentates, and derivatives.) Ligand can also contain N—N Hexadentates) nonbinding N, O, S, or P atoms. N Valence Stabilizer #42: RR′C═N—R″, where R, R′, and R″ Schiff Bases with one represent H, or any organic functional group Imine (C═N) Group and wherein the number of carbon atoms ranges with ortho- or alpha- or from 0 to 40, optionally having halogen or beta-amino or imino or polarizing or water-insolubilizing/ oximo or diazeno or solubilizing groups attached. (Must contain hydrazido substitution ortho- or alpha- or beta-amino or imino or (N—N Bidentates, N—N oximo or diazeno or hydrazido substitution.) Tridentates, N—N Ligand can also contain nonbinding N, O, S, Tetradentates, N—N or P atoms. Pentadentates, or N—N Hexadentates). Also includes hydrazones with ortho-N substitution. N Valence Stabilizer #43: RR′C═N—R″—N═CR″′R″″ or Schiff Bases with two R—N═C—R′—CN—R′ or Imine (C═N) Groups RC═N—R′—N═CR″, where R, R′, R″, and without ortho- (for aryl R″′, and R″″ represent H, or any organic constituents) or alpha- functional group wherein the number of or beta- (for alkyl carbon atoms ranges from 0 to 40, optionally constituents) hydroxy, having halogen or polarizing or water- carboxy, carbonyl, thiol, insolubilizing/solubilizing groups attached. mercapto, thiocarbonyl, (Not including ortho-, alpha-, or beta- amino, imino, oximo, hydroxy, carboxy, carbonyl, thiol, mercapto, diazeno, or hydrazido thiocarbonyl, amino, imino, oximo, diazeno, substitution (N—N or hydrazido substitution.) Ligand can also Bidentates). Also includes contain nonbinding N, O, S, or P atoms. dihydrazones. N Valence Stabilizer #44: RR′C═N—R″—N═CR″′R″″ or Schiff Bases with two R—N═C—R′—C═N—R′ or Imine (C═N) Groups and RC═N—R′—N═CR″, where R, R′, R″, with ortho- or alpha- or R″′, and R″″ represent H, or any organic beta-amino or imino or functional group wherein the number of oximo or diazeno or carbon atoms ranges from 0 to 40, optionally hydrazido substitution having halogen or polarizing or water- (N—N Tridentates, insolubilizing/solubilizing groups attached. N—N Tetradentates, (Must contain ortho- or alpha- or beta-amino N—N Pentadentates, or or imino or oximo or diazeno or hydrazido N—N Hexadentates). substitution.) Ligand can also contain Also includes hydrazones nonbinding N, O, S, or P atoms. with ortho-N substitution. N Valence Stabilizer #45: N(—R—N═CR′R″)3 , where R, R′, and R″ Schiff Bases with three represent H, or any organic functional group Imine (C═N) Groups and wherein the number of carbon atoms ranges without ortho- (for aryl from 0 to 40, optionally having halogen or constituents) or alpha- polarizing or water-insolubilizing/ or beta- (for alkyl solubilizing groups attached. (Not including constituents) hydroxy, ortho-, alpha-, or beta-hydroxy, carboxy, carboxy, carbonyl, thiol, carbonyl, thiol, mercapto, thiocarbonyl, mercapto, thiocarbonyl, amino, imino, oximo, diazeno, or hydrazido amino, imino, oximo, substitution.) Ligand can also contain diazeno, or hydrazido nonbinding N, O, S, or P atoms. substitution (N—N Tridentates). Also includes trihydrazones. N Valence Stabilizer #46: N(—R—N═CR′R″)3, where R, R′, and R″ Schiff Bases with three represent H, or any organic functional group Imine (C═N) Groups and wherein the number of carbon atoms ranges with ortho- or alpha- or from 0 to 40, optionally having halogen or beta-amino or imino or polarizing or water-insolubilizing/ oximo or diazeno or solubilizing groups attached. (Must contain hydrazido substitution ortho- or alpha- or beta-amino or imino or (N—N Tetradentates, oximo or diazeno or hydrazido substitution.) N—N Pentadentates, Ligand can also contain nonbinding N, O, S, or N—N Hexadentates) or P atoms. S Valence Stabilizer #1: Macrocyclic ligands containing two, four, Macrocyclic, or six thioketone binding sites to valence Macrobicyclic, and stabilize the central metal ion. Can include Macropolycyclic other hydrocarbon or ring systems bound to Oligothioketones this macrocyclic ligand, but they do not (including Catapinands, coordinate with the stabilized, high valence Cryptands, Cyclidenes, and metal ion. This ligand and/or attached, Sepulchrates) wherein all uncoordinating hydrocarbons/rings may or Binding Sites are composed may not have halogen or polarizing or of Thioketones (typically water-insolubilizing/solubilizing groups in the beta position) (S—S attached. Bidentates, S—S Tetradentates, and S—S Hexadentates) S Valence Stabilizer #2: Macrocyclic ligands containing two, four, Macrocyclic, six, or eight 1,1-dithiolene binding sites to Macrobicyclic, and valence stabilize the central metal ion. Can Macropolycyclic include other hydrocarbon or ring systems Dithiolenes (including bound to this macrocyclic ligand, but they do Catapinands, Cryptands, not coordinate with the stabilized, high Cyclidenes, and valence metal ion. This ligand and/or Sepulchrates) wherein all attached, uncoordinating hydrocarbons/rings Binding Sites are may or may not have halogen or polarizing composed of alpha, alpha or water-insolubilizing/solubilizing groups dithiols (meaning two thiol attached. groups on a single carbon atom in the ring) (S—S Bidentates, S—S Tetradentates, and S—S Hexadentates) S Valence Stabilizer #3: RC(═S)—NR′—C(═S)—R″ for dithio- Dithiolmidodialdehydes, imidodialdehydes, and RC(═S)—NR′— Dithiohydrazidodialdehydes NH—C(═S)—R″ for dithiohydrazidodi- (thioacyl thiohydrazides), aldehydes (thioacyl thiohydrazides), where R, Bis(dithioimidodi- R′, and R″ represent H, NH2, or any aldehydes), Bis(dithio- organic functional group wherein the number hydrazidodialdehydes), of carbon atoms ranges from 0 to 40, Poly(dithioimidodi- optionally having halogen or polarizing or aldehydes), and Poly(di- water-insolubilizing/solubilizing groups thiohydrazidodialdehydes) attached. Ligand can also contain nonbinding (S—S Bidentates, N, O, S, or P atoms. S—S Tridentates, S—S Tetradentates) S Valence Stabilizer #4: R—O—C(═S)—NR′—C(═S)—O—R″ or Dithioimidodicarbonic R—S—C(═S)—NR′—C(═S)—S—R″ for acids, Dithiohydrazidodi- dithioimidodicarbonic acids, and R—O— carbonic acids, Bis(dithio- C(═S)—NR′—NH—C(═S)—O—R″ or imidodicarbonic acids), R—S—C(═S)—NR′—NH—C(═S)—S— Bis(dithiohydrazidodi- R″ for dithiohydrazidodicarbonic acids, carbonic acids), Poly(di- where R, R′, and R″represent H, NH2, or thioimidodicarbonic acids), any organic functional group wherein the Poly(dithiohydrazidodi- number of carbon atoms ranges from 0 to 40, carbonic acids) and optionally having halogen or polarizing or derivatives thereof water-insolubilizing/solubilizing groups (S—S Bidentates, attached. Ligand can also contain S—S Tridentates, nonbinding N, O, S, or P atoms. S—S Tetradentates) S Valence Stabilizer #5: R—C(═S)—CR′R″—C(═S)—R″′ where 1,3-Dithioketones (Dithio- R, R′, R″, and R″′ represent H, NH2, or beta-ketonates), 1,3,5- any organic functional group wherein the Trithioketones, Bis(1,3- number of carbon atoms ranges from 0 to 40, Dithioketones), and optionally having halogen or polarizing or Poly(1,3-Dithioketones) water-insolubilizing/solubilizing groups (S—S Bidentates, S—S attached. Ligand can also contain Tridentates, S—S nonbinding N, O, S, or P atoms. Tetradentates) S Valence Stabilizer #6: R—C(═S)—C(═S)—R′ where R and R′ 1,2-Dithioketones represent H, NH2, or any organic functional (Dithiolenes, Dithio- group wherein the number of carbon atoms alpha-ketonates), 1,2,3- ranges from 0 to 40, optionally having Trithioketones, halogen or polarizing or water-insolubilizing/ Dithiotropolonates, solubilizing groups attached. Ligand can also ortho-Dithioquinones, contain nonbinding N, O, S, or P atoms. Bis(1,2-Dithioketones), and Poly(1,2-Dithioketones) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) S Valence Stabilizer #7: RR′—N—C(═S)—CR″R″′—C(═S)—N— Dithiomalonamides R″″R′″″where R, R′, R″, R″′,R″″, and R″″′ (Dithiomalonodiamides), represent H, NH2, or any organic functional Bis(dithiomalonamides), group wherein the number of carbon atoms and Polydithiomalonamides ranges from 0 to 40, optionally having (S—S Bidentates, halogen or polarizing or water-insolubilizing/ S—S Tridentates, solubilizing groups attached. Ligand can also S—S Tetradentates) contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #8: RR′—N—C(═S)—CR″R″′—C(═S)—R″″ 2-Thioacylthioacetamides, where R, R′, R″, R″′, and R″″ represent H, Bis(2-thioacylthio- NH2, or any organic functional group acetamides), and Poly(2- wherein the number of carbon atoms ranges thioacylthioacetamides) from 0 to 40, optionally having halogen or (S—S Bidentates, polarizing or water-insolubilizing/ S—S Tridentates, solubilizing groups attached. Ligand can also S—S Tetradentates) contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #9: R—C(═S)—S—C(═S)—R′ where R and Dithioacyl sulfides, R′ represent H or any organic functional Bis(dithioacyl sulfides), group wherein the number of carbon atoms and Poly(dithioacyl ranges from 0 to 40, optionally having sulfides) (S—S halogen or polarizing or water-insolubilizing/ Bidentates, S—S solubilizing groups attached. Ligand can also Tridentates, S—S contain nonbinding N, O, S, or P atoms. Tetradentates) S Valence Stabilizer #10: RR′—N—C(═S)—S—C(═S)—N—R″R″′ Trithiodicarbonic Diamides, where R, R′, R″, and R″′ represent H, NH2 Bis(trithiodicarbonic or any organic functional group wherein the diamides), and Poly(tri- number of carbon atoms ranges from 0 to 40, thiodicarbonic diamides) optionally having halogen or polarizing or (S—S Bidentates, water-insolubilizing/solubilizing groups S—S Tridentates, attached. Ligand can also contain nonbinding S—S Tetradentates) N, O, S, or P atoms. S Valence Stabilizer #11: R—S—C(═S)—S—C(═S)—S—R′ for Pentathio-, Tetrathio-, or pentathiodicarbonic acids, R—O—C(═S)— Trithiodicarbonic Acids, S—C(═S)—S—R′ for tetrathiodicarbonic Bis(pentathio-, tetrathio-, acids, and R—O—C(═S)—S—C(═S)— or trithiodicarbonic acids), O—R′ for pentathiodicarbonic acids, Poly(pentathio-, tetrathio-, where R and R′ represent H, NH2 or any or trithiodicarbonic acids), organic functional group wherein the number and derivatives thereof of carbon atoms ranges from 0 to 40, (S—S Bidentates, optionally having halogen or polarizing or S—S Tridentates, water-insolubilizing/solubilizing groups S—S Tetradentates) attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #12: (R—O—)(R′—O—)P(═S)—P(═S) Dithiohypophosphoric (—O—R″)(—O—R″′); (R—O—)(R′—S—) Acids, Bis(dithiohypo- P(═S)—P(═S)(—S—R″)(—O—R″′); phosphoric acids), and or (R—S—)(R′—S—)P(═S)—P(═S) Poly(dithiohypophosphoric (—S—R″)(—S—R″′), where R, R′, R″, and acids), and derivatives R″′ represent H, NH2 or any organic thereof (S—S Bidentates, functional group wherein the number of S—S Tridentates, carbon atoms ranges from 0 to 40, optionally S—S Tetradentates) having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. Note: these ligands are not to be confused with hypophosphorous acid derivatives (hypophosphites) (R—O—) R″R″′P(═O) which are very reducing and therefore unacceptable for stabilization of high valence states in metal ions. S Valence Stabilizer #13: (RR′—N—)(R″R″′—N—)P(═S)(—N— Dithiohypophosphoramides, R″″R″″′)(—N—R″″″R″″″′), where R, R′, Bis(dithiohypophosphor- R″, R″′, and R″″, R″″′, R″″″, and R″″″′ amides), Poly(dithiohypo- represent H, NH2 or any organic functional phosphoramides) (S—S group wherein the number of carbon atoms Bidentates, S—S ranges from 0 to 40, optionally having Tridentates, S—S halogen or polarizing or water-insolubilizing/ Tetradentates) solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. Note: these ligands are not to be confused with hypophosphorous acid derivatives (hypophosphites) (R—O—)R″R″′P(═O) which are very reducing and therefore unacceptable for stabilization of high valence states in metal ions. S Valence Stabilizer #14: (R—O—)(R′—O—)P(═S)—NH—P(═S) Dithioimidodiphosphoric (—O—R″)(—O—R″′); (R—O—)(R′—S—) Acids, Dithiohydrazidodi- P(═S)—NH—P(═S )(—S—R″)(—O— phosphoric Acids, Bis(di- R″′); or (R—S—)(R′—S—)P(═S)—NH— thioimidodiphosphoric P(═S)(—S—R″)(—S—R″′) for dithio- Acids), Bis(dithiohydra- imidodiphosphoric acids, and —NH—NH— zidodiphosphoric Acids), derivatives for dithiohydrazidodiphosphoric Poly(dithioimidodi- acids, where R, R′, R″, and R″′ represent phosphoric Acids), Poly(di- H, NH2 or any organic functional group thiohydrazidodiphosphoric wherein the number of carbon atoms ranges Acids), and derivatives from 0 to 40, optionally having halogen or thereof (S—S Bidentates, polarizing or water-insolubilizing/ S—S Tridentates, solubilizing groups attached. Ligand can also S—S Tetradentates) contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #15: (RR′—N—)(R″R′″—N—)(═S)—NH— Dithioimidodiphosphor- P(═S)(—N—R″″R″″′)(—N—R″″″R″″″′) amides, Dithiohydrazidodi- for dithioimidophosphoramides, and phosphoramides, Bis(di- (RR ′—N—)(R″R″′—N—)P(═S)—NH— thioimidodiphosphor- NH—P(═S)(—N—R″″R″″′) amides), Bis(dithiohydra- (—N—R″″″R″″″′) for dithiohydrazidodi- zidodiphosphoramides), phosphoramides, where R, R′, R″, R″′, R″″, Poly(dithioimidodiphos- R″″′, R″″″, and R″″″′ represent H, NH2 or phoramides), and Poly(di- any organic functional group wherein the thiohydrazidodiphosphor- number of carbon atoms ranges from 0 to 40, amides) (S—S Bidentates, optionally having halogen or polarizing or S—S Tridentates, water-insolubilizing/solubilizing groups S—S Tetradentates) attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #16: (RR′—N—)(R″R″′—N—)P(═S)—S—P(═S)(—N— Dithiodiphosphoramides, R″″R″″′)(—N—R″″″R″″″′), or (RR′—N—) Bis(dithioiphosphor- (R″R″′—N—)P(═S)—O—P(═S) amides), and Poly(dithio- (—N—R″″″R″″″′), where R, R′, R″, R″′, diphosphoramides) (S—S R″″, R″″′, R″″″, and R″″″′ represent H, Bidentates, S—S NH2 or any organic functional group wherein Tridentates, S—S the number of carbon atoms ranges from 0 to Tetradentates) 40, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #17: (R—O—)(R ′—O—)P(═S)—O— Dithiodiphosphoric Acids, P(═S)(—O—R″)(—O—R″′); Bis(dithioiphosphoric (R—O—)(R ′—O—)P(═S)—S— Acids), Poly(dithiodiphos- P(═S)(—O—R″)(—O—R″′); phoric Acids), and (R—O—)(R ′—O—)P(═S)—O— derivatives thereof P(═S)(—O—R″)(—O—R″′); (S—S Bidentates, (R—O—)(R ′—O—)P(═S)—S— S—S Tridentates, P(═S)(—O—R″)(—O—R″′); or S—S Tetradentates) (R—S—)(R ′—O—)P(═S)—S— P(═S)(—O—R″)(—O—R″′); where R, R′, R″, R″′, R″″, R″″′, R″″″, and R″″″′represent H, NH2 or any organic functional group wherein the number of carbon atoms ranges from 0 to 40, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #18: (O═)P(—S—R)(—S—R′)(—S—R″) or Trithiophosphoric Acids (S═)P(—S—R)(—S—R′)(—O—R″), (Phosphorotrithioic Acids), where R, R′, and R″ represent H, NH2 or any Bis(trithiophosphoric organic functional group wherein the number acids), Poly(trithiophos- of carbon atoms ranges from 0 to 40, phoric acids), and optionally having halogen or polarizing or derivatives thereof water-insolubilizing/solubilizing groups (S—S Bidentates, attached. Ligand can also contain S—S Tridentates, nonbinding N, O, S, or P atoms. S—S Tetradentates) S Valence Stabilizer #19: (O═)P(—S—R)(—S—R′)(—O—R″) or Dithiophosphoric Acids (S═)P(—S—R)(—O—R′)(—O—R″), (Phosphorodithioic Acids), where R, R′, and R″represent H, NH2 or any Bis(dithiophosphoric acids), organic functional group wherein the number Poly(dithiophosphoric of carbon atoms ranges from 0 to 40, acids), and derivatives optionally having halogen or polarizing or thereof (S—S Bidentates, water-insolubilizing/solubilizing groups S—S Tridentates, attached. Ligand can also contain nonbinding S—S Tetradentates) N, O, S, or P atoms. S Valence Stabilizer #20: (S═)P(—S—R)(—S—R′)(—S—R″), where Tetrathiophosphoric Acids R, R′, and R″ represent H, NH2 or any (Phosphorotetrathioic organic functional group wherein the number Acids), Bis(tetrathio- of carbon atoms ranges from 0 to 40, phosphoric acids), optionally having halogen or polarizing or Poly(tetrathiophosphoric water-insolubilizing/solubilizing groups acids), and derivatives attached. Ligand can also contain nonbinding thereof (S—S Bidentates, N, O, S, or P atoms. S—S Tridentates, S—S Tetradentates) S Valence Stabilizer #21: (O═)P(—S—S—R)(—S—R′)(—S—R″) or Phosphoro(dithioperoxo)di- (S)P(—S—S—R)(—S—R′)(—O—R″), thioic Acids, Bis[phos- where R, R′, and R″represent H, NH2 or any phoro(dithioperoxo)dithioic organic functional group wherein the number Acids], Poly[phosphoro(di- of carbon atoms ranges from 0 to 40, thioperoxo)dithioic Acids], optionally having halogen or polarizing or and derivatives thereof water-insolubilizing/solubilizing groups (S—S Bidentates, attached. Ligand can also contain nonbinding S—S Tridentates, N, O, S, or P atoms. S—S Tetradentates) S Valence Stabilizer #22: (O═)P(—S—S—R)(—S—R′)(—O—R″) or Phosphoro(dithio- (S═)P(—S—S—R)(—O—R′)(—O—R″), peroxo)thioic Acids, where R, R′, and R″represent H, NH2 or any Bis[phosphoro(dithio- organic functional group wherein the number peroxo)thioic Acids], of carbon atoms ranges from 0 to 40, Poly[phosphoro(dithio- optionally having halogen or polarizing or peroxo)thioic Acids], water-insolubilizing/solubilizing groups and derivatives thereof attached. Ligand can also contain nonbinding (S—S Bidentates, N, O, S, or P atoms. S—S Tridentates, S—S Tetradentates) S Valence Stabilizer #23: (S═)P(—S—S—R)(—S—R′)(—S—R″), Phosphoro(dithioper- where R, R′, and R″ represent H, NH2 or any oxo)trithioic Acids, organic functional group wherein the number Bis[phosphoro(dithio- of carbon atoms ranges from 0 to 40, peroxo)trithioic Acids], optionally having halogen or polarizing or Poly[phosphoro(dithio- water-insolubilizing/solubilizing groups peroxo)trithioic Acids], attached. Ligand can also contain nonbinding and derivatives thereof N, O, S, or P atoms. (S—S Bidentates, S—S Tridentates, S—S Tetradentates) S Valence Stabilizer #24: R—CR′(—SH)—CH2—C(═S)—R″, where Beta-Mercaptothioketones, R, R′, and R″ represent H, NH2 or any Beta-Mercaptothio- organic functional group wherein the number aldehydes, Bis(beta- of carbon atoms ranges from 0 to 40, mercaptothioketones), optionally having halogen or polarizing or Bis(beta-mercaptothio- water-insolubilizing/solubilizing groups aldehydes), Poly(beta- attached. Ligand can also contain nonbinding mercaptothioketones), N, O, S, or P atoms. and Poly(beta- mercaptothioaldehydes) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) S Valence Stabilizer #25: RR′—N—CH(—SH)—NR″—C(═S)— N-(Aminomethylthiol)thio- NR″′R″″, where R, R′, R″, R″′, and R″″ ureas [N-(Aminomercapto- represent H, NH2 or any organic functional methyl)thioureas], Bis[N- group wherein the number of carbon atoms (aminomethylthiol)thio- ranges from 0 to 40, optionally having ureas], and Poly[N-(amino- halogen or polarizing or water-insolubilizing/ methylthiol)thioureas] solubilizing groups attached. Ligand can also (S—S Bidentates, contain nonbinding N, O, S, or P atoms. S—S Tridentates, S—S Tetradentates) S Valence Stabilizer #26: RR′—N—C(═S)—C(═S)—N—R″R″′, Dithiooxamides, where R, R′, and R″, and R″′ represent H, Bis(dithiooxamides), NH2 or any organic functional group wherein Poly(dithiooxamides) the number of carbon atoms ranges from 0 (S—S Bidentates, to 40, optionally having halogen or S—S Tridentates, polarizing or water-insolubilizing/ S—S Tetradentates) solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #27: RR′—C═C(—S−)(—S−), where R and R′ 1,1-Dithiolates, Bis(1,1- represent H, NH2 or any organic functional dithiolates), and group wherein the number of carbon atoms Poly(1,1-dithiolates) ranges from 0 to 40, optionally having (S—S Bidentates and halogen or polarizing or water-insolubilizing/ S—S Tetradentates) solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #28: R—C(═S)(—S—R′) for dithiomono- Dithiomonocarboxylic carboxylic acids, and (R—S—)(S═)C— Acids, Tri- and Tetrathio- R′—C(═S)(—S—R″) for tri- and tetra- dicarboxylic Acids, thiodicarboxylic acids, where R, R′, and R″ Bis(dithiomonocarboxylic represent H, NH2 or any organic functional Acids), Bis(tri- and tetra- group wherein the number of carbon atoms thiodicarboxylic acids), ranges from 0 to 40, optionally having Poly(dithiomonocarboxylic halogen and or polarizing or water- acids), Poly(tri- and insolubilizing/solubilizing groups attached. tetrathiodicarboxylic Ligand can also contain nonbinding N, O, S, acids), derivatives thereof or P atoms. (S—S Bidentates and S—S Tetradentates) S Valence Stabilizer #29: R—C(═S)(—S—S—R′) for perthiomono- Perthiomonocarboxylic carboxylic acids, and (R—S—S—)(S═)C— Acids, Perthiodicarboxylic R′—C(═S)(—S—S—R″) for perthiodi- Acids, Bis(perthiomono- carboxylic acids, where R, R′, and R″ carboxylic acids), represent H, NH2 or any organic functional Bis(perthiodicarboxylic group wherein the number of carbon atoms acids), Poly(perthiomono- ranges from 0 to 40, optionally having carboxylic acids), halogen or polarizing or water- Poly(perthiodicarboxylic insolubilizing/solubilizing groups attached. acids), and derivatives Ligand can also contain nonbinding N, O, S, thereof (S—S Bidentates or P atoms. and S—S Tetradentates) S Valence Stabilizer #30: R—S—C(═S)—O—R′ or Dithiocarbonates, R—S—C(═O)—S—R′ for dithiocarbonates, Trithiocarbonates, R—S—C(═S)—S—R′ for trithiocarbonates, Perthiocarbonates, and R—S—S—C(═S)—S—R′ for perthio- Bis(dithiocarbonates), carbonates, where R, and R′ represent H, Bis(trithiocarbonates), and NH2 or any organic functional group wherein Bis(perthiocarbonates) the number of carbon atoms ranges from 0 to (S—S Bidentates and 40, optionally having halogen or polarizing S—S Tetradentates) or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #31: RR′N+ ═C(SH)(SH), where R and R′ represent Dithiocarbamates, H, OH, SH, OR″ (R″═C1-C30 alkyl or Bis(dithiocarbamates), aryl), SR″ (R″═C1-C30 alkyl or aryl), and Poly(dithiocarbamates) NH2 or any organic functional group wherein (including N-hydroxydi- the number of carbon atoms ranges from 0 to thiocarbamates and N- 40, optionally having halogen or polarizing mercaptodithiocarbamates) or water-insolubilizing/solubilizing groups (S—S Bidentates, attached. Ligand can also contain nonbinding S—S Tridentates, and N, O, S, or P atoms. S—S Tetradentates) S Valence Stabilizer #32: RR′N—NR″—C(═S)(SH), where R and R′ Dithiocarbazates represent H, NH2 or any organic functional (Dithiocarbazides), group wherein the number of carbon atoms Bis(dithiocarbazates), and ranges from 0 to 40, optionally having Poly(dithiocarbazates) halogen or polarizing or water- (S—S Bidentates, insolubilizing/solubilizing groups S—S Tridentates, and attached. Ligand can also contain nonbinding S—S Tetradentates; or N, O, S, or P atoms. possibly N—S Bidentates, N—S Tridentates, and N—S Tetradentates) S Valence Stabilizer #33: Thiocyanates bound directly to the high Thiocyanate ligands valence metal ion. (S Monodentates) O Valence Stabilizer #1: RR′—N—C(═O)—NR″—C(═O)— Biurets (Imidodicarbonic NR″′R″″ for biurets, and RR′—N— Diamides), Isobiurets, C(═O)—NR″—NH—C(═O)—NR″′R″″ Biureas, Triurets, for biureas, where R, R′, R″, R″′, and R′″′ Triureas, Bis(biurets), represent H, NH2, or any organic functional Bis(isobiurets), group wherein the number of carbon atoms Bis(biureas), Poly(biurets), ranges from 0 to 40, optionally having Poly(isobiurets), halogen or polarizing or water- and Poly(biureas) insolubilizing/solubilizing groups (O—O Bidentates, attached. Ligand can also contain nonbinding O—O Tridentates, N, O, S, or P atoms. O—O Tetradentates) O Valence Stabilizer #2: RR′—N—C(═O)—NR″—C(═O)—R″′ Acylureas, Aroylureas, where R, R′, R″, and R″′ represent H, NH2, Bis(acylureas), or any organic functional group wherein the Bis(aroylureas), number of carbon atoms ranges from 0 to 40, Poly(acylureas), and optionally having halogen or polarizing or Poly(aroylureas) water-insolubilizing/solubilizing groups (O—O Bidentates, attached. Ligand can also contain nonbinding O—O Tridentates, N, O, S, or P atoms. O—O Tetradentates) O Valence Stabilizer #3: RC(═O)—NR′—C(═O)—R″ for Imidodialdehydes, imidodialdehydes, and RC(═O)—NR — Hydrazidodialdehydes NH—C(═O)—R″ for hydrazidodialdehydes (Acyl hydrazides), (acyl hydrazides), where R, R′, and R″ Bis(imidodialdehydes), represent H, NH2, or any organic functional Bis(hydrazidodialdehydes), group wherein the number of carbon atoms Poly(imidodialdehydes), ranges from 0 to 40, optionally having and Poly(hydrazidodi- halogen or polarizing or water- aldehydes) (O—O insolubilizing/solubilizing groups attached. Bidentates, O—O Ligand can also contain nonbinding N, O, S, Tridentates, O—O or P atoms. Tetradentates) O Valence Stabilizer #4: R—O—C(═O)—NR′—C(═O)—O—R″ for Imidodicarbonic acids, imidodicarbonic acids, and R—O— Hydrazidodicarbonic acids, C(═O)—NR′—NH—C(═O)—O—R″ for Bis(imidodicarbonic acids), hydrazidodicarbonic acids, where R, R′, and Bis(hydrazidodicarbonic R″ represent H, NH2, or any organic acids), Poly(imidodi- functional group wherein the number of carbonic acids), carbon atoms ranges from 0 to 40, optionally Poly(hydrazidodicarbonic having halogen or polarizing or water- acids) and derivatives insolubilizing/solubilizing groups attached. thereof (O—O Bidentates, Ligand can also contain nonbinding N, O, S, O—O Tridentates, or P atoms. O—O Tetradentates) O Valence Stabilizer #5: RR′—N—S(═O)(═O)—NR″— Imidodisulfamic Acid, S(═O)(═O)—NR′″R″″ for imidodisulfamic Imidodisulfuric Acid, acid, and R—O—S(═O)(═O)—NR′— Bis(Imidodisulfamic Acid), S(═O)(═O)—OR″ for imidosulfuric acid, Bis(Imidodisulfuric Acid), where R, R′, and R″ represent H, NH2, or Poly(Imidodisulfamic any organic functional group wherein the Acid), and Poly(Imido- number of carbon atoms ranges from 0 to 40, disulfuric Acid) and optionally having halogen or polarizing or derivatives thereof water-insolubilizing/solubilizing groups (O—O Bidentates, attached. Ligand can also contain nonbinding O—O Tridentates, N, O, S, or P atoms. O—O Tetradentates) O Valence Stabilizer #6: R—C(═O)—CR′R″—C(═O)—R″′ where 1,3-Diketones (Beta- R, R′, R″, and R″′ represent H, NH2, or any Diketonates), 1,3,5- organic functional group wherein the number Triketones, Bis(1,3- of carbon atoms ranges from 0 to 40, Diketones), and Poly(1,3- optionally having halogen or polarizing or Diketones), all with a water-insolubilizing/solubilizing groups Molecular Weight Greater attached. Ligand can also contain nonbinding than 125 (O—O Bidentates, N, O, S, or P atoms. If these ligands exhibit O—O Tridentates, a molecular weight less than or equal to 125, O—O Tetradentates) the solubility of the resultant Mn+3- diketonate complex will be too high. O Valence Stabilizer #7: R—C(═O)—C(═O)—R′ where R and R′ 1,2-Diketones (Alpha- represent H, NH2, or any organic functional Diketonates), 1,2,3- group wherein the number of carbon atoms Triketones, Tropolonates, ranges from 0 to 40, optionally having ortho-Quinones, halogen or polarizing or water-insolubilizing/ Bis(1,2-Diketones), and solubilizing groups attached. Ligand can also Poly(1,2-Diketones), all contain nonbinding N, O, S, or P atoms. If with a Molecular Weight these ligands exhibit a molecular weight less Greater than 100 than or equal to 100, the solubility of the (O—O Bidentates, resultant Mn+3-diketonate complex will be O—O Tridentates, too high. O—O Tetradentates) O Valence Stabilizer #8: RR′—N—C(═)—CR″R″′—C(═O)—N— Malonamides R″″R″″′ where R, R′, R″, R″′,R″″, and R″″′ (Malonodiamides), represent H, NH2, or any organic functional Bis(malonamides), and group wherein the number of carbon atoms Polymalonamides ranges from 0 to 40, optionally having (O—O Bidentates, halogen or polarizing or water- O—O Tridentates, insolubilizing/solubilizing groups attached. O—O Tetradentates) Ligand can also contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #9: RR′—N—C(═O)—CR″R″′—C(═O)—R″″ 2-Acylacetamides, where R, R′, R″, R″′, and R″″ represent H, Bis(2-acylacetamides), NH2, or any organic functional group and Poly(2-acylacetamides) wherein the number of carbon atoms ranges (O—O Bidentates, from 0 to 40, optionally having halogen or O—O Tridentates, polarizing or water-insolubilizing/ O—O Tetradentates) solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #10: RR′—N—C(═O)—S—C(═O)—N—R″R″′ Monothiodicarbonic where R, R′, R″, and R″′ represent H, NH2 or Diamides, any organic functional group wherein the Bis(monothiodicarbonic number of carbon atoms ranges from 0 to 40, diamides), and optionally having halogen or polarizing or Poly(monothiodicarbonic water-insolubilizing/solubilizing groups diamides) (O—O attached. Ligand can also contain nonbinding Bidentates, O—O N, O, S, or P atoms. Tridentates, O—O Tetradentates) O Valence Stabilizer #11: R—O—C(═O)—S—C(═O)—O—R′, Monothiodicarbonic Acids, where R and R′ represent H, NH2 or any Bis(monothiodicarbonic organic functional group wherein the number acids), Poly(monothiodi- of carbon atoms ranges from 0 to 40, carbonic acids), and optionally having halogen or polarizing or derivatives thereof water-insolubilizing/solubilizing groups (O—O Bidentates, attached. Ligand can also contain nonbinding O—O Tridentates, N, O, S, or P atoms. O—O Tetradentates) O Valence Stabilizer #12: R—O—S(═O)(═O)—S—S(═O)—O—R′ Trithionic acid, where R and R′ represent H, NH2 or any Bis(trithionic acid), organic and derivatives functional group wherein the Poly(trithionic acid), number of carbon atoms ranges from 0 to 40, thereof (O—O Bidentates, optionally having halogen or polarizing or O—O Tridentates, water-insolubilizing/solubilizing groups O—O Tetradentates) attached. Ligand can also contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #13: (R—O—)(R′—O—)P(═O)— Hypophosphoric Acids, P(═O) (—O—R″)(—O—R′″), where R, Bis(hypophosphoric acids), R′, R″, and R″′ represent H, NH2 or any and Poly(hypophosphoric organic functional group wherein the number acids), and derivatives of carbon atoms ranges from 0 to 40, thereof (O—O Bidentates, optionally having halogen or polarizing or O—O Tridentates, water-insolubilizing/solubilizing groups O—O Tetradentates) attached. Ligand can also contain nonbinding N, O, S, or P atoms. Note: these ligands are not to be confused with hypophosphorous acid derivatives (hypophosphites) (R—O—)R″R″′P(═O) which are very reducing and therefore unacceptable for stabilization of high valence states in metal ions. O Valence Stabilizer #14: (RR′—N—)(RR″R′″—N—)P(═O)— Hypophosphoramides, P(═O)(—N—R″″R″″′)(—N—R″″″R″″″′), Bis(hypophosphoramides), where R, R′, R″, R″′, R″″, R″″′, R″″″, and and Poly(hypophosphor- R″″″′represent H, NH2 or any organic amides) (Q—O Bidentates, functional group wherein the number of O—O Tridentates, carbon atoms ranges from 0 to 40, optionally O—O Tetradentates) having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. Note: these ligands are not to be confused with hypophosphorous acid derivatives (hypophosphites) (R—O—)R″R″′P(═O) which are very reducing and therefore unacceptable for stabilization of high valence states in metal ions. O Valence Stabilizer #15: (R—O—)(R′—O—)P(═O)—NH— Imidodiphosphoric Acids, P(═O)(—O—R″)(—O)—R″′) for Hydrazidodiphosphoric imidodiphosphoric acids, and (R—O—)(R′— Acids, Bis(imidodiphos- O—)P(═O)—NH—NH—P(═O)(—O—R″) phoric Acids), Bis(hydra- (—O—R″′) for hydrazidodiphosphoric zidodiphosphoric Acids), acids; where R, R′, R″, and R″′ represent H, Poly(imidodiphosphoric NH2 or any organic functional group Acids), Poly(hydra- wherein the number of carbon atoms ranges zidodiphosphoric Acids), from 0 to 40, optionally having halogen or and derivatives thereof polarizing or water-insolubilizing/ (O—O Bidentates, solubilizing groups attached. Ligand can also O—O Tridentates, contain nonbinding N, O, S, or P atoms. O—O Tetradentates) O Valence Stabilizer #16: (RR′—N—)(R″R″′—N—)P(═O)—NH— Imidodiphosphoramides, P(═O)(—N—R″″R″″′)(—N—R″″″R″″″′) Hydrazidodiphos- for imidodiphosphoramides, and phoramides, Bis(imidodi- —NH—NH— derivatives for hydrazidodi- phosphoramides), phosphoramides, where R, R′, R″, R″′, R″″, Bis(hydrazidodi- R″″′, R″′″′, and R″″″′ represent H, NH2 or phosphoramides), any organic functional group wherein the Poly(imidodiphos- number of carbon atoms ranges from 0 to 40, phoramides), and optionally having halogen or polarizing or Poly(hydrazidodi- water-insolubilizing/solubilizing groups phosphoramides) attached. Ligand can also contain nonbinding (O—O Bidentates, N, O, S, or P atoms. O—O Tridentates, O—O Tetradentates) O Valence Stabilizer #17: (RR′—N—)(R″R″′—N—)PQ═O)—O— Diphosphoramides, P(═O)(—N—R″″R″″′)(—N—R″″″R″″″′), Bis(diphosphoramides), and where R, R′, R″, R″′, R″″, R″″′, R″″″, and Poly(diphosphoramides) R″″″′ represent H, NH2 or any organic (O—O Bidentates, functional group wherein the number of O—O Tridentates, carbon atoms ranges from 0 to 40, optionally O—O Tetradentates) having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #18: R—CR′(—OH)—CH2—C(═O)—R″, Beta-Hydroxyketones, where R, R′, and R″ represent H, NH2 or Beta-Hydroxyaldehydes, any organic functional group wherein the Bis(beta-hydroxyketones), number of carbon atoms ranges from 0 to 40, Bis(beta- optionally having halogen or polarizing or hydroxyaldehydes), water-insolubilizing/solubilizing groups Poly(beta-hydroxyketones), attached. Ligand can also contain nonbinding and Poly(beta- N, O, S, or P atoms. hydroxyaldehydes) (O—O Bidentates, O—O Tridentates, O—O Tetradentates) O Valence Stabilizer #19: RR′—N—CH(—OH)—NR″—C(═O)— N-(Aminomethylol)ureas NR″′R″″, where R, R′, R″, R″′, and R″″ [N-(Aminohydroxy- represent H, NH2 or any organic functional methyl)ureas], Bis[N- group wherein the number of carbon atoms (aminomethylol)ureas], ranges from 0 to 40, optionally having and Poly[N-(amino- halogen or polarizing or water-insolubilizing/ methylol)ureas] solubilizing groups attached. Ligand can also (O—O Bidentates, contain nonbinding N, O, S, or P atoms. O—O Tridentates, O—O Tetradentates) O Valence Stabilizer #20: RR′—N—C(═O)—C(═O)—N—R″R″′, Oxamides, Bis(oxamides), where R, R′, R″, and R″′ represent H, NH2 or and Poly(oxamides) any organic functional group wherein the (O—O Bidentates, number of carbon atoms ranges from 0 to 40, O—O Tridentates, optionally having halogen or polarizing or O—O Tetradentates) water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #21: —C(—OH)═C(—OH)—, where the two Squaric Acids and carbon atoms supporting the hydroxy groups derivatives thereof are included within a cyclic hydrocarbon (O—O Bidentates) moiety, optionally having halogen or polarizing or water-insolubilizing/ solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #22: (R—O—)(O═)C—R′—C(═O)(—O—R″), Dicarboxylic Acids, where R, R′,and R″ represent H, NH2 or Bis(dicarboxylic acids), any organic functional group wherein the Poly(dicarboxylic acids), number of carbon atoms ranges from 0 to 40, and derivatives thereof optionally having halogen or polarizing or (O—O Bidentates and water-insolubilizing/solubilizing groups O—O Tetradentates) attached. Ligand can also contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #23: RR′N+═C(OH)(OH), where R and R′ Carbamates, represent H, OH, SH, OR″ (R″═C1-C30 Bis(carbamates), and alkyl or aryl), SR″ (R″═C1-C30 alkyl Poly(carbamates) or aryl), NH2 or any organic functional (including N- group wherein the number of carbon atoms hydroxycarbamates and ranges from 0 to 40, optionally having N-mercaptocarbamates) halogen or polarizing or water-insolubilizing/ (O—O Bidentates, solubilizing groups attached. Ligand can also O—O Tridentates, and contain nonbinding N, O, S, or P atoms. O—O Tetradentates) O Valence Stabilizer #24: RN═C(OH)(OH), where R represents H, Carbimates, NH2 or any organic functional group wherein Bis(carbimates), and the number of carbon atoms ranges from 0 to Poly(carbimates) 40, optionally having halogen or polarizing (O—O Bidentates, or water-insolubilizing/solubilizing groups O—O Tridentates, an attached. Ligand can also contain nonbinding O—O Tetradentates) N, O, S, or P atoms. O Valence Stabilizer #25: Cyanates bound directly to the high valence Cyanate ligands metal ion. (O Monodentates) N—S Valence RR′—N—C(═NH)—S—S—C(═NH)— Stabilizer #1: NR″R″′, where R, R′, R″, and R″′ represent Diformamidine Disulfides H, NH2, or any organic functional group (Thioperoxydicarbonimidic wherein the number of carbon atoms ranges Diamides or Dihydrazides), from 0 to 40, optionally having halogen or Thioperoxytricarbonimidic polarizing or water-insolubilizing/ Diamides or Dihydrazides, solubilizing groups attached. Ligand can also Thioperoxytetra- contain nonbinding N, O, S, or P atoms. carbonimidic Diamides or Dihydrazides, Bis(diformamidine disulfides), and Poly(diformamidine disulfides) (N—S Bidentates, N—S Tridentates, N—S Tetradentates) N—S Valence RR′—N—C(═NH)—S—CS—NR″R″′, Stabilizer #2: where R, R′, R″, and R″′ represent H, NH2 or S-Amidinodithio- any organic functional group wherein the carbamates, Bis(S-amidino- number of carbon atoms ranges from 0 to 40, dithiocarbamates), and optionally having halogen or polarizing or Poly(S- amidinodithio- water-insolubilizing/solubilizing groups carbamates) (N—S attached. Ligand can also contain nonbinding Bidentates and N, O, S, or P atoms. N—S Tetradentates) N—S Valence RR′—N—C(═NH)—O—CS—NR″R″′, Stabilizer #3: where R, R′, R″, and R″′ represent H, NH2 or O-Amidinothiocarbamates, any organic functional group wherein the Bis(O-amidinothio- number of carbon atoms ranges from 0 to 40, carbamates), and Poly(O- optionally having halogen or polarizing or amidinothiocarbamates) water-insolubilizing/solubilizing groups (N—S Bidentates and attached. Ligand can also contain nonbinding N—S Tetradentates) N, O, S, or P atoms. N—S Valence RR′—N—C(═NH)—S—S—CS—NR″R″′, Stabilizer #4: where R, R′, R″, and R″′ represent H, NH2 or S-Amidinoperoxythio- any organic functional group wherein the carbamates, Bis(S-amidino- number of carbon atoms ranges from 0 to 40, peroxythiocarbamates), and optionally having halogen or polarizing or Poly(S-amidinoperoxythio- water-insolubilizing/solubilizing groups carbamates) (N—S attached. Ligand can also contain nonbinding Bidentates and N—S N, O, S, or P atoms. Tetradentates) N—S Valence (NH═)P(—SR)(—OR′)(—OR″) for Stabilizer #5: phosphorimidothioic acid, (NH═)P(═SR) Phosphorimidothioic Acid; (═SR′)(OR″) for phosphorimidodithioic Phosphorimidodithioic acid, (NH═)P(—SR)(—SR′)(—SR″) for Acid; Phosphorimidotri- phosphorimidotrithioic acid, where R, R′, thiole Acid; Bis(Phos- and R″ represent H, NH2 or any organic phorimidothioic Acid); functional group wherein the number of Bis(Phosphorimidodithioic carbon atoms ranges from 0 to 40, optionally Acid); Bis(Phosphorimido- having halogen or polarizing or water- trithioic Acid); Poly(Phos- insolubilizing/solubilizing groups attached. phorimidothioic Acid); Ligand can also contain nonbinding N, Poly(Phosphorimidodithioic O, S, or P atoms. Acid); Poly(Phosphor- imidotrithioic Acid); and derivatives thereof (N—S Bidentates and N—S Tetradentates) N—S Valence (S═)P(—NRR′)(—NR″R″′)(—NR″″R″″′), Stabilizer #6: where R, R′, R″, R″′, R″″, and R″″′ represent Phosphorothioic Triamides, H, NH2 or any organic functional group Bis(phosphorothioic wherein the number of carbon atoms ranges triamides), and Poly(phos- from 0 to 40, optionally having halogen or phorothioic triamides) polarizing or water-insolubilizing/ (N—S Bidentates solubilizing groups attached. Ligand can also and N—S Tetradentates) contain nonbinding N, O, S, or P atoms. N—S Valence (S═)P(—NRR′)(—SR″)(—SR″′) for Stabilizer #7: phosphoramidotrithioic acid, and Phosphoramidotrithioic (S═)P(—NRR ′)(—NR″R″′)(—SR″″) for Acid, Phosphorodiamido- phosphorodiamidodithioic acid, where R, R′, dithioic Acid, R″, R″′, and R″″represent H, NH2 or any Bis(phosphoramido- organic functional group wherein the number trithioic acid), of carbon atoms ranges from 0 to 40, Bis(phosphorodiamido- optionally having halogen or polarizing or dithioic acid), water-insolubilizing/solubilizing groups poly(phosphoramido- attached. Ligand can also contain nonbinding trithioic acid), N, O, S, or P atoms. poly(phosphorodiamido- dithioic acid), and derivatives thereof (N—S Bidentates and N—S Tetradentates) N—S Valence (O═)P(—NRR′)(—SR″)(—OR″′) or Stabilizer #8: (S═)P(—NRR′)(—OR″)(—OR″′) for Phosphoramidothioic Acid, phosphoramidothioic acid; Phosphoramidodithioic (O═)P(—NRR′)(—SR″)(—SR″′) or Acid, Phosphorodi- (S═)P(—NRR′)(—SR″)(—OR″′) for amidothioic Acid, phosphoramidodithioic acid; Bis(Phosphoramido- (O═)P(—NRR′NR″R″′)(—SR″″) or thioic Acid), (S═)P(—NRR′)(—NR″R″′)(—OR″″) for Bis(Phosphoramido- phosphorodiamidothioic acid, where R, R′, dithioic Acid), R″, R″′, and R″″represent H, NH2 or any Bis(Phosphorodi- organic functional group wherein the number amidothioic Acid), of carbon atoms ranges from 0 to 40, Poly(Phosphoramido- optionally having halogen or polarizing or thioic Acid), water-insolubilizing/solubilizing groups Poly(Phosphoramido- attached. Ligand can also contain nonbinding dithioic Acid), and N, O, S, or P atoms. Poly(Phosphorodi- amidothioic Acid) (N—S Bidentates and N—S Tetradentates) N—S Valence R′—C(═S)—N═C(—R)(—NHR″), where Stabilizer #9: R is an aromatic derivative (i.e. —C6H5), N-Thioacyl and R′and R″ represent H, NH2, or any 7-Aminobenzylidenimines organic functional group wherein the number (N—S Bidentates or of carbon atoms ranges from 0 to 40, N—S Tetradentates) optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—S Valence R—C(═S)—NR′—OH or Stabilizer #10: R—C(—SH)═N—OH, where R and R′ Thiohydroxamates represent H, NH2, or any organic functional (Thiohydroxylamines), group wherein the number of carbon atoms Bis(thiohydroxamates), and ranges from 0 to 40, optionally having Poly(thiohydroxamates) halogen or polarizing or water-insolubilizing/ (N—S Bidentates, solubilizing groups attached. Ligand can also N—S Tetradentates, contain nonbinding N, O, S, or P atoms. and N—S Hexadentates) N—S Valence R—CH(—NHR′)—C(═S)(—OH) or Stabilizer #11: R—CH(—NHR′)—C(═5)(—SH) for Alpha- or ortho- aminothiocarboxylic acids, and Aminothiocarboxylic (HO—)(S═)C—CH(—NHR)—R′—CH(— Acids, and alpha- or ortho- NHR″)—C(═S)(—OH) or (HS—)(S═)C— Aminothiodicarboxylic CH(—NHR)—R′—CH(—NHR″)— Acids, and derivatives C(═S)(—SH) for aminothiodicarboxylic thereof (N—S Bidentates, acids, where R, R′, and R″represent any N—S Tridentates, organic functional group wherein the and N—S Tetradentates) number of carbon atoms ranges from 1 to 40, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—S Valence RR′—N—C(═S)—NR″—N═CR″′R″″, Stabilizer #12: where R, R′, R″, R″′, and R″″ represent H, Thiosemicarbazones, or any organic functional group wherein the Bis(thiosemicarbazones), number of carbon atoms ranges from 0 to 40, and Poly(thiosemi- optionally having halogen or polarizing or carbazones) (N—S water-insolubilizing/solubilizing groups Bidentates, N—S attached. Ligand can also contain nonbinding Tetradentates, and N, O, S, or P atoms. N—S Hexadentates) N—S Valence R—C(═S)—NR′—N═CR″R″′, where R, Stabilizer #13: R′, R″, and R″′ represent H, or any organic Thioacyl hydrazones, functional group wherein the number of Bis(thioacyl hydrazones), carbon atoms ranges from 0 to 40, optionally and Poly(thioacyl having halogen or polarizing or water- hydrazones) insolubilizing/solubilizing groups attached. (N—S Bidentates, Ligand can also contain nonbinding N, O, N—S Tetradentates, S, or P atoms. and N—S Hexadentates) N—S Valence R—N═N—C(═S)—NR′—NR″R″′, where Stabilizer #14: R, R′, R″, R″′ represent H, or any organic Thiocarbazones functional group wherein the number of (Diazenecarbothioic and carbon atoms ranges from 0 to 40, optionally hydrazides), having halogen or polarizing or water- Bis(thiocarbazones), and insolubilizing/solubilizing groups attached. Poly(thiocarbazones) Ligand can also contain nonbinding N, O, (N—S Bidentates, S, or P atoms. N—S Tetradentates, and N—S Hexadentates) N—S Valence R—N═N—R′ for azo compounds, Stabilizer #15: R—N═N—NH—R′ for triazenes, where R, Azo compounds including and R′ represent H or any organic functional triazenes with thiol or group wherein the number of carbon atoms mercapto or thiocarbonyl ranges from 0 to 40, optionally having substitution at the ortho- halogen or polarizing or water-insolubilizing/ (for aryl) or alpha- or beta- solubilizing groups attached. (Must include (for alkyl) positions, ortho-thio, mercapto, or thiocarbonyl Bis[o-(HS-) or alpha- substituted aryl azo compounds, and alpha- or beta-(HS-)azo or beta-thio, mercapto, or thiocarbonyl alkyl compounds], or azo compounds.) Ligand can also contain Poly[o-(HS-) or alpha- nonbinding N, O, S, or P atoms. or beta-(HS-)azo compounds) (N—S Bidentates, N—S Tridentates, N—S Tetradentates, or N—S Hexadentates) N—S Valence R—N═N—C(═S)—N′R′R″ Stabilizer #16: for diazeneformothioamides, and Diazeneformothioamides, R—N═N—CR′R″—C(═S)—NR″′R″″ Diazeneacetothioamides, for diazeneacetothioamides, where R, R′, R″, Bis(diazene- R″′, and R″″ represent H, NH2, or any formothioamides), organic functional group wherein the number Bis(diazene- of carbon atoms ranges from 0 to 40, acetothioamides), optionally having halogen or polarizing or Poly(diazene- water-insolubilizing/solubilizing groups formothioamides), and attached. Ligand can also contain nonbinding Poly(diazene- N, O, S, or P atoms. acetothioamides) (N—S Bidentates, N—S Tetradentates, and N—S Hexadentates) N—S Valence R—N═N—C(═S)—O—R′ or Stabilizer #17: R—N═N—CR′R″—C(═S)—O—R″′ Diazenecarbothioic acids, for diazenecarbothioic acids, and Diazenecarbodithioic acids, R—N═N—C(═S)—S—R′ or Bis(diazene- R—N═N—CR′R″—C(═′S)—S—R″′ carbothioic acids), for diazenecarbodithoic acids, where R, R′, Bis(diazene- R″, and R″′ represent H, NH2, or any carbodithioic acids), organic functional group wherein the number Poly(diazene- of carbon atoms ranges from 0 to 40, carbothioic acids), optionally having halogen or polarizing or Poly(diazene- water-insolubilizing/solubilizing groups carbodithioic acids) and attached. Ligand can also contain nonbinding derivatives thereof N, O, S, or P atoms. (N—S Bidentates, N—S Tetradentates, N—S Hexadentates) N—S Valence R—N═N—C(═S)—R′for Stabilizer #18: diazeneformothioaldehydes, and Diazeneformo- R—N═N—CR′R″—C(═S)—R″′ for thioaldehydes, diazeneacetothioaldehydes, where R, R′, R″, Diazeneaceto- and R″′ represent H, NH2, or any organic thioaldehydes, functional group wherein the number of Bis(diazeneformo- carbon atoms ranges from 0 to 40, optionally thioaldehydes), having halogen or polarizing or water- Bis(diazeneaceto- insolubilizing/solubilizing groups attached. thioaldehydes), Ligand can also contain nonbinding N, O, S, Poly(diazeneformo- or P atoms. thioaldehydes), and Poly(diazeneaceto- thioaldehydes) (N—S Bidentates, N—S Tetradentates and N—S Hexadentates) N—S Valence RR′—N—C(═S)—N═N—C(═S)— Stabilizer #19: NR″R′″ or RR′—N—C(═S)— Diazenediformothioamides, N═N—C(═O)—NR″R″′ for Diazenediacetothioamides, diazenediformothioamides, and RR′—N— Bis(diazenedi- C(═S)—CR″R″′—N═N—CR″″R″″′— formothioamides), C(═S)—NR″″″R″″″′ or Bis(diazenedi- RR′—N—C(═S)—CR″R′″—N═N— acetothioamides), CR″″R″″′—C(═O)—NR″″″R″″″′ Poly(diazenedi- for diazenediacetothioamides, where R, R′, formothioamides), and R″, R″′, R″″, R″″′, R″″″, and R″″″′ represent Poly(diazenedi- H, NH2, or any organic functional group acetothioamides) wherein the number of carbon atoms ranges (N—S Tridentates from 0 to 40, optionally having halogen or and N—S Hexadentates) polarizing or water-insolubilizing/ solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—S Valence R—O—C(═S)—N═N—C(═S)—O—R′, Stabilizer #20: R—O—C(═S)—CR′R″—N═N— Diazenedicarbothioic acids, CR′″R″″—C(═S)—O—R″″′, Diazenedi- R—O—C(═S)—N═N—C(═O)—O—R′, carbodithioic acids, or R—O—C(═S)—CR′R″—N═′N— Bis(diazenedi- CR″′R″″—C(═O)—O—R″″′ for carbothioic acids), diazenedicarbothioic acids, and R—S— Bis(diazenedi- C(═S)—N═N—C(═S)—S—R′ or carbodithioic acids), R—S—C(═S)—CR′R″—N═N— Poly(diazenedi- CR″′R″″—C(═S)—S—R″″′ for carbothioic acids), diazenedicarbodithoic acids, where R, R′, Poly(diazenedi- R″, R″′, R″″, and R″′″ represent H, NH2, carbodithioic acids) and or any organic functional group wherein the derivatives thereof number of carbon atoms ranges from 0 to 40, (N—S Tridentates optionally having halogen or polarizing or and N—S Hexadentates) water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—S Valence RC(═S)—N═N—C(═S)—R′ or Stabilizer #21: RC(═S)—N═N—C(═O)—R′ for Diazenedi- diazenediformothioaldehydes, and RC(═S)— formothioaldehydes, CR′R″—N═N—CR″′R″″—C(═S)—R′″″ or Diazenedi- RC(═S)—CR′R″—N═N—CR″′R″″— acetothioaldehydes, C(═O)—R″″′ for diazenediaceto- Bis(diazenedi- thioaldehydes, where R, R′, R″, R″′, R″″, formothioaldehydes), and R″″′ represent H, NH2, or any organic Bis(diazenedi- functional group wherein the number of acetothioaldehydes), carbon atoms ranges from 0 to 40, optionally Poly(diazenedi- having halogen or polarizing or water- formothioaldehydes), and insolubilizing/solubilizing groups attached. Poly(diazenedi- Ligand can also contain nonbinding N, O, S, acetothioaldehydes) or P atoms. (N—S Tridentates and N—S Hexadentates) N—S Valence R—N═N—CR′═N—NR″R″′, where R, Stabilizer #22: R′, R″, and R″′ represent H, or any organic Ortho-thio (or -mercapto) functional group wherein the number of Substituted Formazans, carbon atoms ranges from 0 to 40, optionally Bis(o-thio or -mercapto having halogen or polarizing or water- substituted formazans), insolubilizing/solubilizing groups and Poly(o-thio or attached. (Must include ortho-thio or -mercapto substituted mercapto substituted aryl R derivatives, formazans) (N—S and beta-thio or mercapto substituted alkyl Bidentates, N—S R derivatives.) Ligand can also contain Tridentates, N—S nonbinding N, O, S, or P atoms. Tetradentates, and N—S Hexadentates) N—S Valence RR′C═N—NC═R″R″′ or Stabilizer #23: RR′C═N—NR″R″′ (for ketazines), Ortho-thio (or -mercapto) where R, R′, R″, and R″′ represent H, or any Substituted Azines organic functional group wherein the number (including ketazines), of carbon atoms ranges from 0 to 40, Bis(o-thio or mercapto optionally having halogen or polarizing or substituted azines), and water-insolubilizing/solubilizing groups Poly(o-thio or mercapto attached. (Must include ortho-thio or substituted azines) mercapto substituted aryl R derivatives, (N—S Bidentates, and beta-thio or mercapto substituted alkyl N—S Tridentates, R derivatives.) Ligand can also contain N—S Tetradentates, nonbinding N, O, S, or P atoms. and N—S Hexadentates) N—S Valence RR′C═N—R″, where R, R′, and R″ Stabilizer #24: represent H, or any organic functional group Schiff Bases with one wherein the number of carbon atoms ranges Imine (C═N) Group and from 0 to 40, optionally having halogen or with ortho- or alpha- or polarizing or water-insolubilizing/ beta-thio or mercapto or solubilizing groups attached. (Must contain thiocarbonyl substitution ortho- or alpha- or beta- thio or mercapto (N—S Bidentates, or thiocarbonyl substitution.) Ligand can also N—S Tridentates, contain nonbinding N, O, S, or P atoms. N—S Tetradentates, N—S Pentadentates, or N—S Hexadentates). Also includes Schiff Bases derived from the reaction of carbonyl compounds with dithiocarbazates, and hydrazones with ortho-S substitution. N—S Valence RR′C═N—R″—N═CR″′R″″ or Stabilizer #25: R—N═C—R′—C═N—R′ or Schiff Bases with two RC═N—R′—N═CR″, where R, R′, R″, Imine (C═N) Groups R″′, and R″″ represent H, or any organic and with ortho- or alpha- functional group wherein the number of or beta-thio or mercapto or carbon atoms ranges from 0 to 40, optionally thiocarbonyl substitution having halogen or polarizing or water- (N—S Tridentates, insolubilizing/solubilizing groups attached. N—S Tetradentates, (Must contain ortho- or alpha- or beta-thio or N—S Pentadentates, mercapto or thiocarbonyl substitution.) or N—S Hexadentates). Ligand can also contain nonbinding N, O, S, Also includes Schiff Bases or P atoms. derived from the reaction of carbonyl compounds with dithiocarbazates, and hydrazones with ortho-S substitution. N—S Valence N(—R—N═CR′R″)3, where R, R′, and R″ Stabilizer #26: represent H, or any organic functional group Schiff Bases with three wherein the number of carbon atoms ranges Imine (C═N) Groups and from 0 to 40, optionally having halogen or with ortho- or alpha- or polarizing or water-insolubilizing/ beta- thio or mercapto or solubilizing groups attached. (Must contain thiocarbonyl substitution ortho- or alpha- or beta-thio or mercapto or (N—S Tetradentates, thiocarbonyl substitution.) Ligand can also N—S Pentadentates, contain nonbinding N, O, S, or P atoms. or N—S Hexadentates). Also includes Schiff Bases derived from the reaction of carbonyl compounds with dithiocarbazates, and hydrazones with ortho-S substitution. N—S Valence [R—CR′(—NR″R″′)]x—R″″—[C(— Stabilizer #27: SR″″′)R″″″R″″″′]y , [R—CR′(—NR″R″′)]x— Thioalkyl Amines R″″—[C(—S—S—R″″′)R″″″R″″″′]y, or (Aminothiols or [R—CR′(—NR″R″′)]x—R″″— Aminodisulfides) and LC(═S)R″″′]y for thioalkyl amines; and Thioalkyl Imines [R—C(═NR′)]x—R″—[C(— (Iminothiols or SR″′)R″″R″″′]y, [R—C(═NR′)]x—R″— Iminodisulfides) [C(—S—[C(═S)R″′]y for thioalkyl imines, (N—S Bidentates, where R, R′, H, NH2, or any organic N—S Tridentates, functional group wherein the number of N—S Tetradentates, and carbon atoms ranges from 0 to 40, optionally N—S Hexadentates) having halogen or polarizing or water- insolubilizing/solubilizing groups attached, and x and y = 1-6. Ligand can also contain nonbinding N, O, S, or P atoms. N—S Valence [R(—NR′R″)(—SR″′)], Stabilizer #28: [R(—NR′R″)(—S—S—R″′)], Thioaryl Amines and [R(—NR′R″)(—C(═S)R″′], Thioaryl Imines (N—S [R(—NR′R″)x]2S, Bidentates, N—S [R(—NR′R″)x]2−3R″′(—SR′″′)y , Tridentates, N—S [R(—SR′)x]2−3R″(—NR″′R″″)y, Tetradentates, and [R(—NR′R″)x]2S2, and N—S Hexadentates) [R(—NR′R″)x]2R″′(C(═S))yR″″ for thioaryl amines; and [R(—SR′)x]NH or [R(—SR′)x]2NHNH for thioaryl imines, where R, R′, R″, R″′, and R″″ represent H, NH2, or any organic functional group wherein the number of carbon atoms ranges from 0 to 40, optionally having halogen or polanzing or water- insolubilizing/solubilizing groups attached, and x = 0-2 and y = 1-4. Ligand can also contain nonbinding N, O, S, or P atoms. N—S Valence Five membered heterocyclic ring(s) Stabilizer #29: containing one, two, three, or four nitrogen Five-Membered atoms. In addition, ligand contains additional Heterocyclic Rings sulfur-containing substituents (usually thiols, containing One, Two, mercaptans, disulfides, or thiocarbonyls) that Three, or Four Nitrogen constitute S binding sites. Can include other Atoms at least one ring systems bound to the heterocyclic ring additional Sulfur Atom or to the S-containing substituent, but they Binding Site not in a Ring do not coordinate with the stabilized, high (N—S Bidentates, valence metal ion. Ring(s) can also contain N—S Tridentates, O, S, or P atoms. This 5-membered ring(s) N—S Tetradentates, and/or attached, uncoordinating rings and/or or N—S Hexadentates) S-containing substituent(s) may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. N—S Valence Six membered heterocyclic ring(s) Stabilizer #30: containing one, two, three, or four nitrogen Six-Membered atoms. In addition, ligand contains additional Heterocyclic Rings sulfur-containing substituents (usually thiols, containing One, Two, mercaptans, disulfides, or thiocarbonyls) that Three, or Four Nitrogen constitute S binding sites. Can include other Atoms at least one ring systems bound to the heterocyclic ring additional Sulfur Atom or to the S-containing substituent, but they Binding Site not in a Ring do not coordinate with the stabilized, high (N—S Bidentates, valence metal ion. Ring(s) can also contain N—S Tridentates, O, S, or P atoms. This 6-membered ring(s) N—S Tetradentates, and/or attached, uncoordinating rings and/or or N—S Hexadentates) S-containing substituent(s) may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. N—S Valence Five membered heterocyclic ring(s) Stabilizer #31: containing one or two sulfur atoms. In Five-Membered addition, ligand contains additional nitrogen- Heterocyclic Rings containing substituents (usually amines, containing One or Two imines, or hydrazides) that constitute N Sulfur Atoms at least one binding sites. Can include other ring systems additional Nitrogen Atom bound to the heterocyclic ring or to the Binding Site not in a Ring N-containing substituent, but they do not (N—S Bidentates, coordinate with the stabilized, high valence N—S Tridentates, metal ion. Ring(s) can also contain O, S, N—S Tetradentates, or P atoms. This 5-membered ring(s) and/or or N—S Hexadentates) attached, uncoordinating rings and/or N-containingsubstituent(s) may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. N—S Valence Six membered heterocyclic ring(s) Stabilizer #32: containing one or two sulfur atoms. In Six-Membered addition, ligand contains additional nitrogen- Heterocyclic Rings containing substituents (usually amines, containing One or Two imines, or hydrazides) that constitute N Sulfur Atoms at least one binding sites. Can include other ring systems additional Nitrogen Atom bound to the heterocyclic ring or to the Binding Site not in a Ring N-containing substituent, but they do not (N—S Bidentates, coordinate with the stabilized, high valence N—S Tridentates, metal ion. Ring(s) can also contain O, S, or N—S Tetradentates, P atoms. This 6-membered ring(s) and/or or N—S Hexadentates) attached, uncoordinating rings and/or N-containingsubstituent(s) may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. N—S Valence Five membered heterocyclic ring(s) Stabilizer #33: containing one, two, three, or four nitrogen Five-Membered atoms. In addition, ligand contains additional Heterocyclic Rings sulfur-containing rings that constitute S containing One, Two, binding sites. Can include other ring systems Three, or Four Nitrogen bound to the N- or S-containing heterocyclic Atoms at least one rings, but they do not coordinate with the additional Sulfur Atom stabilized, high valence metal ion. Ring(s) Binding Site in a Separate can also contain O, S, or P atoms. This Ring (N—S Bidentates, 5-membered ring(s) and/or additional N—S Tridentates, S-containing ring(s) and/or attached, N—S Tetradentates) uncoordinating rings may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. N—S Valence Six membered heterocyclic ring(s) Stabilizer #34: containing one, two, three, or four nitrogen Six-Membered atoms. In addition, ligand contains additional Heterocyclic Rings sulfur-containing rings that constitute S containing One, Two, binding sites. Can include other ring systems Three, or Four Nitrogen bound to the N- or S- containing heterocyclic Atoms at least one rings, but they do not coordinate with the additional Sulfur Atom stabilized, high valence metal ion. Ring(s) Binding Site in a Separate can also contain O, S, or P atoms. This Ring (N—S Bidentates, 6-membered ring(s) and/or additional N—S Tridentates, S-containing ring(s) and/or attached, N—S Tetradentates) uncoordinating rings may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. N—S Valence Macrocyclic ligands containing two, three, Stabilizer #35: four, six, eight, or ten binding sites Two-, Three-, Four-, composed of nitrogen and sulfur to valence Six-, Eight-, and Ten- stabilize the central metal ion. Can include Membered Macrocyclics, other hydrocarbon or ring systems bound to Macrobicyclics, and this macrocyclic ligand, but they do not Macropolycyclics coordinate with the stabilized, high valence (including Catapinands, metal ion. This ligand and/or attached, Cryptands, Cyclidenes, and uncoordinating hydrocarbons/rings may or Sepulchrates) wherein all may not have halogen or polarizing or water- Binding Sites are composed insolubilizing/solubilizing groups attached. of Nitrogen (usually amine or imine groups) or Sulfur (usually thiols, mercaptans, or thiocarbonyls) and are not contained in Component Heterocyclic Rings (N—S Bidentates, N—S Tridentates, N—S Tetradentates, and N—S Hexadentates) N—S Valence Macrocyclic ligands containing a total of Stabilizer #36: four, six, eight, or ten heterocyclic rings Four-, Six-, Eight-, containing and nitrogen or sulfur bindingc or Ten-Membered sites. Can include other hydrocarbon/ring Macrocyclics, systems bound to this macrocyclic ligand, Macrobicyclics, but they do not coordinate with the Macropolycyclics stabilized, high valence metal ion. This (including Catapinands, ligand and/or attached, uncoordinating Cryptands, Cyclidenes, hydrocarbon/rings may or may not have and Sepulchrates) halogen or polarizing or water-insolubilizing wherein all Binding Sites groups attached. are composed of Nitrogen or Sulfur and are contained in Component Heterocyclic Rings (N—S Bidentates, N—S Tridentates, N—S Tetradentates, or N—S Hexadentates) N—S Valence Macrocyclic ligands containing at least one Stabilizer #37: heterocyclic ring. These heterocyclic rings Four-, Six-, Eight-, provide nitrogen or sulfur binding sites to or Ten-Membered valence stabilize the central metal ion. Other Macrocyclics, amine, imine, thiol, mercapto, or Macrobicyclics, and thiocarbonyl binding sites can also be Macropolycyclics included in the macrocyclic ligand, so long (including Catapinands, as the total number of binding sites is four, Cryptands, Cyclidenes, six, eight, or ten. Can include other and Sepulchrates) hydrocarbon/ring systems bound to this wherein all Binding Sites macrocyclic ligand, but they do not are composed of Nitrogen coordinate with the stabilized, high valence or Sulfur and are contained metal ion. This ligand and/or attached, in a Combination of uncoordinating hydrocarbon/rings may or Heterocyclic Rings and may not have halogen or polarizing or water- Amine, Imine, Thiol, insolubilizing groups attached. Mercapto, or Thiocarbonyl Groups (N—S Bidentates, N—S Tridentates, N—S Tetradentates, or N—S Hexadentates) N—O Valence R′—N(—OH)—C(—R)═N—R″, where R, Stabilizer #1: R′, and R″ represent H or any organic N—Hydroxy(or N,N′- functional group wherein the number of dihydroxy)amidines and carbon atoms ranges from 0 to 40, optionally N—Hydroxy(or N,N′- having halogen or polarizing or water-insol dihydroxy)diamidines ubilizing/solubilizing groups attached. (N—O Bidentates, Ligand can also contain nonbinding N, O, S, N—O Tridentates, or P atoms. or N—O Tetradentates) N—O Valence RR′—N—C(═NH)—NR″—CO—NR″′R″″ Stabilizer #2: for guanylureas, and RR′—N—C(═NH)— Guanylureas, NR″—NH—CO—NR″′R″″ for Guanidinoureas, guanidinoureas, where R, R′, R″, R″′, and Bis(guanylureas), R″″ represent H, NH2, or any organic Bis(guanidinoureas), functional group wherein the number of Poly(guanylureas), and carbon atoms ranges from 0 to 40, optionally Poly(guanidinoureas) having halogen or polarizing or water- (N—O Bidentates and insolubilizing/solubilizing groups attached. N—O Tetradentates) Ligand can also contain nonbinding N, O, S, or P atoms. N—O Valence RR′—N—C(═NH)—NR″—CO—R″′ for Stabilizer #3: N-amidinoamides, or RR′—N—C(═NH)— Amidinoamides, CR″R″′—CO—N—R″″R″″′ Guanidinoamides, for 2-amidinoacetamides, and Bis(amidinoamides), RR′—N—C(═NH)—NR″—NH—CO—R″′ Bis(guanidinoamides), for guanidinoamides, where R, R′, R″, R″′, Poly(amidinoamides), and R″″, and R″″′ represent H, NH2, or Poly(guanidinoamides) any organic functional group wherein the (including both N- number of carbon atoms ranges from 0 to 40, amidinoamides and optionally having halogen or polarizing or 2-amidinoacetamides) water-insolubilizing/solubilizing groups (N—O Bidentates attached. Ligand can also contain nonbinding and N—O Tetradentates) N, O, S, or P atoms. N—O Valence R—C(═NH)—NR′—CO—R″, where R, Stabilizer #4: R′, and R″, and R′″ represent H or any Imidoylamides, organic functional group wherein the number Bis(imidoylamides), of carbon atoms ranges from 0 to 40, Poly(imidoylamides) optionally having halogen or polarizing or (N—O Bidentates and water-insolubilizing/solubilizing groups N—O Tetradentates) attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—O Valence RR′—N—C(═NH)—O—CO—NR″R″′, Stabilizer #5: where R, R′, R″, and R″′ represent H, NH2, O-Amidinocarbamates, or any organic functional group wherein the Bis(O-amidinocarbamates), number of carbon atoms ranges from 0 to 40, and Poly(O- optionally having halogen or polarizing or amidinocarbamates) water-insolubilizing/solubilizing groups (N—O Bidentates and attached. Ligand can also contain nonbinding N—O Tetradentates) N, O, S, or P atoms. N—O Valence RR′—N—C(═NH)—S—CO—NR″R″′, Stabilizer #6: where R, R′, R″, and R″′ represent H, NH2, 5-Amidinothiocarbamates, or any organic functional group wherein the Bis(S-amidinothio- number of carbon atoms ranges from 0 to 40, carbamates), and Poly(S- optionally having halogen or polarizing or amidinothiocarbamates) water-insolubilizing/solubilizing groups (N—O Bidentates and attached. Ligand can also contain nonbinding N—O Tetradentates) N, O, S, or P atoms. N—O Valence (NH═)(NH═)P(OR)(OR′), where R, R′, and Stabilizer #7: R″ represent H, NH2, or any organic Diimidosulfuric Acid, functional group wherein the number of Bis(diimidosulfuric carbon atoms ranges from 0 to 40, optionally acid), and derivatives having halogen or polarizing or water- thereof (N—O insolubilizing/solubilizing groups attached. Bidentates and N—O Ligand can also contain nonbinding N, O, S, Tetradentates) or P atoms. N—O Valence (NH═)P(—OR)(—OR′)(—OR″), where R, Stabilizer #8: R′, and R″ represent H, NH2, or any organic Phosphorimidic Acid, functional group wherein the number of Bis(phosphorimidic acid); carbon atoms ranges from 0 to 40, optionally and Poly(phosphorimidic having halogen or polarizing or water- acid), and derivatives insolubilizing/solubilizing groups attached. thereof (N—O Bidentates) Ligand can also contain nonbinding N, O, S, or P atoms. N—O Valence (O═)P(—NRR′)(—NR″R″′)(—NR″″R″″′), Stabilizer #9: where R, R′, R″, R″′, R″″, and R″″′ represent H, Phosphoric Triamides, NH2, or any organic functional group Bis(phosphoric triamides), wherein the number of carbon atoms ranges and Poly(phosphoric from 0 to 40, optionally having halogen or triamides) (N—O polarizing or water-insolubilizing/ Bidentates and solubilizing groups attached. Ligand can also N—O Tetradentates) contain nonbinding N, O, S, or P atoms. N—O Valence (O═)P(—NRR′)(—OR″)(—OR″′) Stabilizer #10: for phosphoramidic acid and (O═)P(— Phosphoramidic Acid, NRR′)(—NR″R″′)(—OR″″) for Phosphorodiamidic Acid, phosphorodiamidic acid, where R, R′, R″, Bis(phosphoramidic acid), R″′, and R″″represent H, NH2, or any Bis(phosphorodiamidic organic functional group wherein the number acid), Poly(phosphor- of carbon atoms ranges from 0 to 40, amidic acid), Poly(phosp- optionally having halogen or polarizing or horodiamidic acid), and water-insolubilizing/solubilizing groups derivatives thereof attached. Ligand can also contain nonbinding (N—O Bidentates N, O, S, or P atoms. and N—O Tetradentates) N—O Valence R′—C(═O)—N═C(—R)(—NHR″), where Stabilizer #11: R is an aromatic derivative (i.e. —C6H5), N-Acyl 7-Aminobenzyl- and R′and R″ represent H, NH2, or any idenimines (N—O organic functional group wherein the number Bidentates or of carbon atoms ranges from 0 to 40, N—O Tetradentates) optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—O Valence R—C(═NOH)—R′ for oximes, and Stabilizer #12: R—C(═NOH)—C(═NOH)—R′ for Oximes, Dioximes, dioximes, where R and R′ represent H, NH2, and Poly(oximes) or any organic functional group wherein the (N—O Bidentates, number of carbon atoms ranges from 0 to 40, N—O Tridentates, optionally having halogen or polarizing or and N—O Tetradentates) water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—O Valence R—C(═O)—C(═NOH)—R′, where R and Stabilizer #13: R′ represent H, NH2, or any organic Carbonyl oximes, functional group wherein the number of Bis(carbonyl oximes), carbon atoms ranges from 0 to 40, optionally and Poly(carbonyl oximes) having halogen or polarizing or water- (N—O Bidentates, insolubilizing/solubilizing groups attached. N—O Tridentates, Ligand can also contain nonbinding N, O, S, and N—O Tetradentates) or P atoms. N—O Valence R—C(═N—R″)—C(═NOH)—R′, where Stabilizer #14: R, R′, and R″ represent H, NH2, or any Imine oximes, organic functional group wherein the Bis(imine oximes), and number of carbon atoms ranges from 0 to 40, Poly(imine oximes) optionally having halogen or polarizing or (including 2-nitrogen water-insolubilizing/solubilizing groups heterocyclic oximes) attached. Ligand can also contain nonbinding (N—O Bidentates, N, O, S, or P atoms. N—O Tridentates, N—O Tetradentates, and N—O Hexadentates) N—O Valence R—CH(—OH)—C(═NOH)—R′, where R, Stabilizer #15: R′, and R″ represent H, NH2, or any Hydroxy oximes, organic functional group wherein the number Bis(hydroxy oximes), and of carbon atoms ranges from 0 to 40, Poly(hydroxy oximes) optionally having halogen or polarizing or (including 2-oxygen water-insolubilizing/solubilizing groups heterocyclic oximes) attached. Ligand can also contain nonbinding (N—O Bidentates, N, O, S, or P atoms. N—O Tridentates, N—O Tetradentates, and N—O Hexadentates) N—O Valence RR′—C(—NH—R″)—C(═NOH)—R′″ Stabilizer #16: where R, R′, R″, and R″′represent H, NH2, Amino oximes, or any organic functional group wherein the Bis(amino oximes), and number of carbon atoms ranges from 0 to 40, Poly(amino oximes) optionally having halogen or polarizing or (N—O Bidentates, water-insolubilizing/solubilizing groups N—O Tridentates, attached. Ligand can also contain nonbinding N—O Tetradentates, N, O, S, or P atoms. and N—O Hexadentates) N—O Valence RR′—N—C(═NOH)—R″, where R, R′, Stabilizer #17: and R″ represent H, NH2, or any organic Amido oximes, functional group wherein the number of Bis(amido oximes), and carbon atoms ranges from 0 to 40, optionally Poly(amido oximes) having halogen or polarizing or water- (N—O Bidentates, insolubilizing/solubilizing groups attached. N—O Tridentates, Ligand can also contain nonbinding N, O, S, N—O Tetradentates, or P atoms. and N—O Hexadentates) N—O Valence R—N═N—C(═NOH)—R′ or RR′C— Stabilizer #18: ═N—NR″—C(═NOH)—R″′, where R, Azo oximes, R′, R″, and R″′represent H, NH2, or any Bis(azo oximes), organic functional group wherein the and Poly(azo oximes) number of carbon atoms ranges from 0 to 40, (N—O Bidentates, optionally having halogen or polarizing or N—O Tridentates, water-insolubilizing/solubilizing groups N—O Tetradentates, attached. (R is typically an aryl group.) and N—O Hexadentates). Ligand can also contain nonbinding N, O, S, Also includes or P atoms. hydrazone oximes. N—O Valence o-(ON—)(HO-)Ar, where Ar represents an Stabilizer #19: aromatic group or heterocyclic wherein the 2—Nitrosophenols number of carbon atoms ranges from 6 to 40, (o-Quinone monoximes) optionally having halogen or polarizing or (N—O Bidentates) water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—O Valence o-(O2N—)(HO-)Ar, where Ar represents an Stabilizer #20: aromatic group or heterocyclic wherein the 2—Nitrophenols number of carbon atoms ranges from 6 to 40, (N—O Bidentates) optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—O Valence R—C(═O)—NR′—OH or Stabilizer #21: R—C(—OH)═N—OH, where R and R′ Hydroxamates represent H, NH2, or any organic functional (Hydroxylamines), group wherein the number of carbon atoms Bis(hydroxamates), and ranges from 0 to 40, optionally having Poly(hydroxamates) halogen or polarizing or water- (N—O Bidentates, insolubilizing/solubilizing groups N—O Tetradentates, attached. Ligand can also contain nonbinding and N—O Hexadentates) N, O, S, or P atoms. N—O Valence R—N(—NO)—OH, where R represents Stabilizer #22: any organic functional group wherein the N-Nitrosohydroxylamines, number of carbon atoms ranges from 1 to 40, Bis(N-nitrosohydroxyl- optionally having halogen or polarizing or amines), and Poly(N- water insolubilizing/solubilizing groups nitrosohydroxylamines) attached. (R is typically an aryl or (N—O Bidentates, heterocyclic group.) Ligand can also contain N—O Tetradentates, nonbinding N, O, S. or P atoms. and N—O Hexadentates) N—O Valence R—CH(—NHR′)—C(═O)(—OH) for Stabilizer #23: amino acids and ortho-aminocarboxylic Amino Acids and acids, and R—CH(—NHR′)—C(═O)— ortho-Aminocarboxylic (NR″—)CH(—R″′)—C(═O)(—OH) Acids, Peptides, for peptides, where R, R′, R″, and R″′ Polypeptides, and Proteins represent any organic functional group [N—O Bidentates, wherein the number of carbon atoms ranges N—O Tridentates, and from 1 to 40, optionally having halogen or N—O Tetradentates; polarizing or water-insolubilizing/ possibly S—O dentates solubilizing groups attached. Ligand can also for sulfur-contg. examples contain nonbinding N, O, S, or P atoms. such as penicillamine and cystine] N—O Valence RCONR′R″, where R, R′, and R″ represent Stabilizer #24: H, NH2, or any organic functional group Amides, Bis(amides), wherein N—O the number of carbon atoms and Poly(amides), ranges from 0 to 40, optionally having including lactams halogen or polarizing or water- (N—O Bidentates, insolubilizing/solubilizing groups Tridentates, and attached. Ligand can also contain nonbinding N—O Tetradentates) N, O, S, or P atoms. N—O Valence RR′—N—C(═O)—NR″—N═CR″′R″″, Stabilizer #25: where R, R′, R″, R″′, and R″″ represent H, Semicarbazones, or any organic functional group wherein the Bis(semicarbazones), and number of carbon atoms ranges from 0 to 40, Poly(semicarbazones) optionally having halogen or polarizing or (N—O Bidentates, water-insolubilizing/solubilizing groups N—O Tetradentates, and attached. Ligand can also contain nonbinding N—O Hexadentates) N, O, S, or P atoms. N—O Valence R—C(═O)—NR′—N═CR″R″′, where Stabilizer #26: R, R′, R″, and R″′ represent H, or any Acyl hydrazones, organic functional group wherein the number Bis(acyl hydrazones), and of carbon atoms ranges from 0 to 40, Poly(acyl hydrazones) optionally having halogen or polarizing or (N—O Bidentates, water-insolubilizing/solubilizing groups N—O Tetradentates, attached. Ligand can also contain nonbinding and N—O Hexadentates) N, O, S, or P atoms. N—O Valence R—N═N—C(═O)—NR′—N—R″R″′, Stabilizer #27: where R, R′, R″, and R″′ represent H, or any Carbazones organic functional group wherein the number (Diazenecarboxylic of carbon atoms ranges from 0 to 40, hydrazides), optionally having halogen or polarizing or Bis(carbazones), and water-insolubilizing/solubilizing groups Poly(carbazones) attached. Ligand can also contain nonbinding (N—O Bidentates, N, O, S, or P atoms. N—O Tetradentates, and N—O Hexadentates) N—O Valence R—N═N—R′ for azo compounds, Stabilizer #28: R—N═N—NH—R′ for triazenes, where R, Azo compounds including and R′ represent H or any organic functional triazenes with hydroxyl group wherein the number of carbon atoms or carboxy or carbonyl ranges from 0 to 40, optionally having substitution at the ortho- halogen or polarizing or water- (for aryl) or alpha- or beta- insolubilizing/solubilizing groups (for alkyl) positions, attached. (Must include ortho-hydroxy or Bis[o-(HO—) or alpha- carboxy or carbonyl substituted aryl azo or beta-(HO—)azo compounds, and alpha- or beta-hydroxy or compounds], or carboxy or carbonyl alkyl azo compounds.) Poly[o-(HO—) or alpha- Ligand can also contain nonbinding N, O, S, or beta-(HO—)azo or P atoms. compounds) (N—O Bidentates, N—O Tridentates, N—O Tetradentates, or N—O Hexadentates) N—O Valence R—N═N—C(═O)—NR′R″ Stabilizer #29: for diazeneformamides, and Diazeneformamides, R—N═N—CR′R″—C(═O)—NR′″R ″″ Diazeneacetamides, for diazeneacetamides, where R, R′, R″, R″′, Bis(diazeneformamides), and R″″ represent H, NH2, or any organic Bis(diazeneacetamides), functional group wherein the number of Poly(diazeneformamides), carbon atoms ranges from 0 to 40, optionally and Poly(diazene- having halogen or polarizing or water- acetamides) insolubilizing/solubilizing groups attached. (N—O Bidentates, Ligand can also contain nonbinding N, O, S, N—O Tetradentates, or P atoms. and N—O Hexadentates) N—O Valence R—N═N—C(═O)—O—R′ Stabilizer #30: for diazeneformic acid, and Diazeneformic acids, R—N═N—CR′R″—C(═O)—O—R″′ Diazeneacetic acids, for diazeneacetic acid, where R, R′, R″, and Bis(diazeneformic acids), R″′ represent H, NH2, or any organic Bis(diazeneacetic acids), functional group wherein the number of Poly(diazeneformic acids), carbon atoms ranges from 0 to 40, optionally Poly(diazeneacetic acids), having halogen or polarizing or water- and derivatives thereof insolubilizing/solubilizing groups attached. (N—O Bidentates, Ligand can also contain nonbinding N, O, S, N—O Tetradentates, or P atoms. N—O Hexadentates) N—O Valence R—N═N—C(═O)—R′ Stabilizer #31: for diazeneformaldehydes, and Diazeneformaldehydes, R—N═N—CR′R″—C(═O)—R″′ for Diazeneacetaldehydes, diazeneacetaldehydes, where R, R′, R″, and Bis(diazene- R″′ represent H, NH2, or any organic formaldehydes), functional group wherein the number of Bis(diazene- carbon atoms ranges from 0 to 40, optionally acetaldehydes), having halogen or polarizing or water- Poly(diazene- insolubilizing/solubilizing groups attached. formaldehydes), and Ligand can also contain nonbinding N, O, S, Poly(diazene- or P atoms. acetaldehydes) (N—O Bidentates, N—O Tetradentates and N—O Hexadentates) N—O Valence RR′—N—C(═O)—NN—C(═O)—NR″R″′ Stabilizer #32: for diazenediformamides, and RR′—N— Diazenediformamides, C(═O)—CR″R″′—N═N—CR″″R″″′— Diazenediacetamides, C(═O)—NR″″″R″″″′for diazenedi- Bis(diazenedi- acetamides, where R, R′, R″, R″′, R″″, R″″′, formamides), R″″″, and R″″″′ represent H, NH2, or any Bis(diazene- organic functional group wherein the diacetamides), number of carbon atoms ranges from Poly(diazenedi- 0 to 40, optionally having halogen or formamides), and polarizing or water-insolubilizing/ Poly(diazenedi- solubilizing groups attached. Ligand can also acetamides) contain nonbinding N, O, S, or P atoms. (N—O Tridentates and N—O Hexadentates) N—O Valence R—O—C(═O)—N═N—C(═O)—O—R′ Stabilizer #33: for diazenediforrnic acid, and Diazenediformic acids, R—O—C(═O)—CR′R″N═N—CR″′R″″— Diazenediacetic acids, C(═O)—R′″″ for diazenediacetic acid, Bis(diazenediformic acids), where R, R′, R″, R″′, R″″, and R″″′ represent Bis(diazenediacetic acids), H, NH2, or any organic functional group Poly(diazenediformic wherein the number of carbon atoms ranges acids), Poly(diazene- from 0 to 40, optionally having halogen or diacetic acids) and polarizing or water-insolubilizing/ derivatives thereof solubilizing groups attached. (N—O Tridentates Ligand can also contain nonbinding and N—O Hexadentates) N, O, S, or P atoms. N—O Valence RC(═O)—N═N—C(═O)—R′ Stabilizer #34: for diazenediformaldehydes, and Diazenediformaldehydes, RC(═O)—CR ′R″—N═N—CR″′R″″— Diazenediacetaldehydes, C(═O)—R″″′ for diazenediacetaldehydes, Bis(diazenedi- where R, R′, R″, R″′, R″″, and R″″′ represent formaldehydes), H, NH2, or any organic functional group Bis(diazenedi- wherein the number of carbon atoms ranges acetaldehydes), from 0 to 40, optionally having halogen or Poly(diazenedi- polarizing or water-insolubilizing/ formaldehydes), and solubilizing groups attached. Ligand can Poly(diazenedi- also contain nonbinding N, O, S, or acetaldehydes) P atoms. (N—O Tridentates and N—O Hexadentates) N—O Valence R—N═N—CR′═N—NR″R″′, where Stabilizer #35: R, R′, R″, and R″′ represent H, or any Ortho-hydroxy (or organic functional group wherein the number -carboxy) Substituted of carbon atoms ranges from 0 to 40, Formazans, Bis(o-hydroxy optionally having halogen or polarizing or or -carboxy substituted water-insolubilizing/solubilizing groups formazans), and attached. (Must include ortho-hydroxy or Poly(o-hydroxy or -carboxy carboxy substituted aryl R derivatives, and substituted formazans) beta-hydroxy or carboxy substituted alkyl R (N—O Bidentates, derivatives.) Ligand can also contain N—O Tridentates, nonbinding N, O, S, or P atoms. N—O Tetradentates, and N—O Hexadentates) N—O Valence RR′C═N—N═CR″R″′or Stabilizer #36: RR′C═N—NR″R″′(for ketazines), where Ortho-hydroxy (or R, R′, R″, and R″′ represent H, or any -carboxy) Substituted organic functional group wherein the number Azines (including of carbon atoms ranges from 0 to 40, ketazines), Bis(o- optionally having halogen or polarizing or hydroxy or carboxy water-insolubilizing/solubilizing groups substituted azines), and attached. (Must include ortho-hydroxy or Poly(o-hydroxy or carboxy substituted aryl R derivatives, carboxy substituted azines) and beta- hydroxy or carboxy substituted (N —O Bidentates, alkyl R derivatives.) Ligand can also contain N—O Tridentates, nonbinding N, O, S, or P atoms. N—O Tetradentates, and N—O Hexadentates) N—O Valence RR′C═N—R″, where R, R′, and R″ Stabilizer #37: represent H, or any organic functional group Schiff Bases with wherein the number of carbon atoms ranges one Imine (C═N) Group from 0 to 40, optionally having halogen or and with ortho- or alpha- polarizing or water-insolubilizing/ or beta-hydroxy or carboxy solubilizing groups attached. (Must contain or carbonyl substitution ortho- or alpha- or beta- hydroxy or carboxy (N—O Bidentates, or carbonyl substitution.) Ligand can also N—O Tridentates, contain nonbinding N, O, S, or P atoms. N—O Tetradentates, N—O Pentadentates, or N—O Hexadentates). Also includes hydrazones with ortho-O substitution. N—O Valence RR′C═N—R″—N═CR″′R″″ or Stabilizer #38: R—N═C—R′—C═N—R′ or Schiff Bases with RC═N—R′—N═CR″, where R, R′, R″, two Imine (C═N) Groups R″′, and R″″ represent H, or any organic and with ortho- or alpha- functional group wherein the number of or beta-hydroxy or carboxy carbon atoms ranges from 0 to 40, optionally or carbonyl substitution having halogenor polarizing or water- (N—O Tridentates, insolubilizing/solubilizing groups attached. N—O Tetradentates, (Must contain ortho- or alpha- or beta- N—O Pentadentates, or hydroxy or carboxy or carbonyl substitution.) N—O Hexadentates). Ligand can also contain nonbinding N, O, S, Also includes hydrazones or P atoms. with ortho-O substitution. N—O Valence N(—R—N═CR′R″)3, where R, R′, and R″ Stabilizer #39: represent H, or any organic functional group Schiff Bases with wherein the number of carbon atoms ranges three Imine (C═N) from 0 to 40, optionally having halogen or Groups and with ortho- polarizing or water-insolubilizing/ or alpha- or beta- solubilizing groups attached. (Must contain hydroxy or carboxy or ortho- or alpha- or beta-hydroxy or carboxy carbonyl substitution or carbonyl substitution.) Ligand can also (N—O Tetradentates, contain nonbinding N, O, S, or P atoms. N—O Pentadentates, or N—O Hexadentates). Also includes hydrazones with ortho-O substitution. N—O Valence [R—C(NR′R″)]x—R″—[Si(—OR″′)zR″″3−z]y Stabilizer #40: where R, R′, R″, R″′, and R″″ represent H, Silylaminoalcohols NH2, or any organic functional group (N—O Bidentates, wherein the number of carbon atoms ranges N—O Tridentates, from 0 to 40, optionally having halogen or N—O Tetradentates, polarizing or water-insolubilizing/ and N—O Hexadentates) solubilizing groups attached, and x and y = 1-6, z =1-3. Ligand can also contain nonbinding N, O, S, or P atoms. N—O Valence [R—C(═NR′)]x—R″—[C(—OR″′)R″″R″″′]y Stabilizer #41: or [R—C(═NR′)]x—R″—[C(═O)R″′]y, Hydroxyalkyl Imines where R, R′, R″, R″′, R″″, and R″″′ represent (Imino Alcohols) H, NH2, or any organic functional group (N—O Bidentates, wherein the number of carbon atoms ranges N—O Tridentates, from 0 to 40, optionally having halogen N—O Tetradentates, or polarizing or water-insolubilizing/ and N—O Hexadentates) solubilizing groups attached, and x and y = 1-6. Ligand can also contain nonbinding N, O, S, or P atoms. N—O Valence [R(—NR′R″)(—OR″′)], Stabilizer #42: [R(—NR′R″)(—C(═O)R″′], Hydroxyaryl Amines [R(—NR′R″)x]2O, and Hydroxyaryl Imines [R(—NR′R″)x]2−3R″′(—OR′″′)y, (N—O Bidentates, [R(—OR′)x]2−3R″(—NR″′R″″)y, and N—O Tridentates, [R(—NR′R″)x]2R″″(C(═O))yR″″ for N—O Tetradentates, hydroxyaryl amines; and [R(—OR′)x]2NH or and N—O Hexadentates) [R(—OR′)x]2NHNH for hydroxyaryl imines, where R, R′, R″, R″′, and R″″ represent H, NH2, or any organic functional group wherein the number of carbon atoms ranges from 0 to 40, optionally having halogen or polarizing or water-insolubilizing/ solubilizing groups attached, and x = O-2 and y = 1-4. Ligand can also contain nonbinding N, O, S, or P atoms. N—O Valence Five membered heterocyclic ring(s) Stabilizer #43: containing one, two, three, or four nitrogen Five-Membered atoms. In addition, ligand contains additional Heterocyclic Rings oxygen-containing substituents (usually containing One, Two, hydroxy, carboxy or carbonyl groups) that Three, or Four Nitrogen constitute O binding sites. Can include other Atoms at least one ring systems bound to the heterocyclic ring additional Oxygen Atom or to the O-containing substituent, but they Binding Site not in a Ring do not coordinate with the stabilized, high (N—O Bidentates, valence metal ion. Ring(s) can also contain N—O Tridentates, O, S, or P atoms. This 5-membered ring(s) N—O Tetradentates, and/or attached, uncoordinating rings and/or or N—O Hexadentates) O-containing substituent(s) may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. N—O Valence Six membered heterocyclic ring(s) Stabilizer #44: containing one, two, three, or four nitrogen Six-Membered atoms. In addition, ligand contains additional Heterocyclic Rings oxygen-containing substituents (usually containing One, Two, hydroxy, carboxy, or carbonyl groups) that Three, or Four Nitrogen constitute O binding sites. Can include other Atoms at least one ring systems bound to the heterocyclic ring additional Oxygen Atom or to the O-containing substituent, but they Binding Site not in a Ring do not coordinate with the stabilized, high (N—O Bidentates, valence metal ion. Ring(s) can also contain N—O Tridentates, O, S, or P atoms. This 6-membered ring(s) N—O Tetradentates, and/or attached, uncoordinating rings and/or or N—O Hexadentates) O-containing substituent(s) may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. N—O Valence Five membered heterocyclic ring(s) Stabilizer #45: containing one or two oxygen atoms. In Five-Membered addition, ligand contains additional nitrogen- Heterocyclic Rings containing substituents (usually amines, containing One or imines, or hydrazides) that constitute N Two Oxygen Atoms at binding sites. Can include other ring systems least one additional bound to the heterocyclic ring or to the Nitrogen Atom Binding N-containing substituent, but they do not Site not in a Ring coordinate with the stabilized, high valence (N—O Bidentates, metal ion. Ring(s) can also contain O, S, N—O Tridentates, or P atoms. This 5-membered ring(s) and/or N—O Tetradentates, attached, uncoordinating rings and/or or N—O Hexadentates) N-containing substituent(s) may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. N—O Valence Six membered heterocyclic ring(s) Stabilizer #46: containing one or two oxygen atoms. In Six-Membered addition, ligand contains additional nitrogen- Heterocyclic Rings containing substituents (usually amines, containing One or imines, or hydrazides) that constitute N Two Oxygen Atoms at binding sites. Can include other ring systems least one additional bound to the heterocyclic ring or to the Nitrogen Atom Binding N-containing substituent, but they do not Site not in a Ring coordinate with the stabilized, high valence (N—O Bidentates, metal ion. Ring(s) can also contain O, S, or N—O Tridentates, P atoms. This 6-membered ring(s) and/or N—O Tetradentates, attached, uncoordinating rings and/or or N—O Hexadentates) N-containingsubstituent(s) may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. N—O Valence Five membered heterocyclic ring(s) Stabilizer #47: containing one, two, three, or four nitrogen Five-Membered atoms. In addition, ligand contains additional Heterocyclic Rings oxygen-containing rings that constitute O containing One, Two, binding sites. Can include other ring systems Three, or Four bound to the N- or O-containing heterocyclic Nitrogen Atoms at rings, but they do not coordinate with the least one additional stabilized, high valence metal ion. Ring(s) Oxygen Atom Binding can also contain O, S, or P atoms. This Site in a Separate Ring 5-membered ring(s) and/or additional O— (N—O Bidentates, containing ring(s) and/or attached, N—O Tridentates, uncoordinating rings may or may not have N—O Tetradentates) halogen or polarizing or water- insolubilizing/solubilizing groups attached. N—O Valence Six membered heterocyclic ring(s) Stabilizer #48: containing one, two, three, or four nitrogen Six-Membered atoms. In addition, ligand contains additional Heterocyclic Rings oxygen-containing rings that constitute O containing One, binding sites. Can include other ring systems Two, Three, or Four bound to the N- or O- containing heterocyclic Nitrogen Atoms at rings, but they do not coordinate with the least one additional stabilized, high valence metal ion. Ring(s) Oxygen Atom Binding can also contain O, S, or P atoms. This Site in a Separate Ring 6-membered ring(s) and/or additional (N—O Bidentates, O-containing ring(s) and/or attached, N—O Tridentates, uncoordinating rings may or may not have N—O Tetradentates) halogen or polarizing or water- insolubilizing/solubilizing groups attached. N—O Valence Macrocyclic ligands containing two, three, Stabilizer #49: four, six, eight, or ten binding sites Two-, Three-, Four-, composed of nitrogen and oxygen to valence Six-, Eight-, and Ten- stabilize the central metal ion. Can include Membered Macrocyclics, other hydrocarbon or ring systems bound to Macrobicyclics, this macrocyclic ligand, but they do not and Macropolycyclics coordinate with the stabilized, high valence (including Catapinands, metal ion. This ligand and/or attached, Cryptands, Cyclidenes, and uncoordinating hydrocarbons/rings may or Sepulchrates) wherein all may not have halogen or polarizing or water- Binding Sites are insolubilizing/solubilizing groups attached. composed of Nitrogen (usually amine or imine groups) or Oxygen (usually hydroxy, carboxy, or carbonyl groupss) and are not contained in Component Heterocyclic Rings (N—O Bidentates, N—O Tridentates, N—O Tetradentates, and N—O Hexadentates) N—O Valence Macrocyclic ligands containing a total of Stabilizer #50: four, six, eight, or ten heterocyclic rings Four-, Six-, Eight-, containing nitrogen or oxygen binding sites. or Ten-Membered Can include other hydrocarbon/ring systems Macrocyclics, bound to this macrocyclic ligand, but they Macrobicyclics, and do not coordinate with the stabilized, high Macropolycyclics valence metal ion. This ligand and/or (including Catapinands, attached, uncoordinating hydrocarbon/rings Cryptands, Cyclidenes, may or may not have halogen or polarizing and Sepulchrates) or water-insolubilizing groups attached. wherein all Binding Sites are composed of Nitrogen or Oxygen and are contained in Component Heterocyclic Rings (N—O Bidentates, N—O Tridentates, N—O Tetradentates, or N—O Hexadentates) N—O Valence Macrocyclic ligands containing at least one Stabilizer #51: heterocyclic ring. These heterocyclic rings Four-, Six-, Eight-, provide nitrogen or oxygen binding sites to or Ten-Membered valence stabilize the central metal ion. Other Macrocyclics, amine, imine, hydroxy, carboxy, or carbonyl Macrobicyclics, and binding sites can also be included in the Macropolycyclics macrocyclic ligand, so long as the total (including Catapinands, number of binding sites is four, six, eight, Cryptands, Cyclidenes, or ten. Can include other hydrocarbon/ring and Sepulchrates) systems bound to this macrocyclic ligand, wherein all Binding but they do not coordinate with the Sites are composed of stabilized, high valence metal ion. Nitrogen or Oxygen and This ligand and/or attached, are contained in a uncoordinating hydrocarbon/rings may or Combination of may not have halogen or polarizing or Heterocyclic Rings and water-insolubilizing groups attached. Amine, Imine, Hydroxy, Carboxy, or Carbonyl Groups (N—O Bidentates, N—O Tridentates, N—O Tetradentates, or N—O Hexadentates) S—O Valence R—C(═S)—CR′R″—C(═O)—R″′ where Stabilizer #1: R, R′, R″, and R″′ represent H, NH2, or any 1,3-Monothioketones organic functional group wherein the number (Monothio-beta- of carbon atoms ranges from 0 to 40, ketonates), optionally having halogen or polarizing or 1,3,5-Monothioketones, water-insolubilizing/solubilizing groups 1,3,5-Dithioketones, attached. Ligand can also contain nonbinding Bis(1,3-Monothioketones), N, O, S, or P atoms. and Poly(1,3- Monothioketones) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) S—O Valence R—C(═S)—CR′E″—C(═O)—R″′ where Stabilizer #2: R, R′, R″, R″′, R″″, and R″″′ represent H, Thiomalonamides NH2, or any organic functional group (Thiomalonodiamides), wherein the number of carbon atoms ranges Bis(thiomalonamides), and from 0 to 40, optionally having halogen or Polythiomalonamides polarizing or water-insolubilizing/ (S—O Bidentates, solubilizing groups attached. Ligand can also S—O Tridentates, contain nonbinding N, O, S, or P atoms. S—O Tetradentates) S—O Valence RR′—N—C(═O)—CR″R″′—C(═S)—R″″ Stabilizer #3: for 2-thioacylacetamides, and 2-Thioacylacetamides, 2- RR′—N—C(═S)—CR″R″′—C(═O)—R″″ Acylthioacetamides, for 2-acylthioacetamides, where R, R′, R″, Bis(2-thioacyl- R″′, and R″″ represent H, NH2, or any acetamides), organic functional group wherein the number Bis(2acylthio- of carbon atoms ranges from 0 to 40, acetamides), Poly(2- optionally having halogen or polarizing or thioacylacetamides), and water-insolubilizing/solubilizing groups Poly(2-Acylthio- attached. Ligand can also contain acetamides) nonbinding N, O, S, or P atoms. (S—O Bidentates, S—O Tridentates, S—O Tetradentates) S—O Valence RR′—N—C(═S)—S—C(═O)—N—R″R″′ Stabilizer #4: where R, R′, R″, and R″′ represent H, NH2 or Dithiodicarbonic any organic functional group wherein the Diamides, number of carbon atoms ranges from 0 to 40, Bis(dithiodicarbonic optionally having halogen or polarizing or diamides), and water-insolubilizing/solubilizing groups Poly(dithiodicarbonic attached. Ligand can also contain nonbinding diamides) (S—O N, O, S, or P atoms. Bidentates, S—O Tridentates, S—O Tetradentates) S—O Valence (R—O—)(R′—O—)P(═S)— Stabilizer #5: P(═O)(—O—R′)(—O—R′″); Monothiohypophos- (R—O—)(R′—S—)P(═S)— phoric Acids, P(═O)(—S—R″)(—O—R″′); or Bis(monothiohypo- (R—S—)(R′—S—)P(═S)— phosphoric acids), and P(═O)(—S—R″)(—S—R″′), Poly(monothiohypo- where R, R′, R″, and R″′ represent H, NH2 or phosphoric acids), and any organic functional group wherein the derivatives thereof number of carbon atoms ranges from 0 to 40, (S—O Bidentates, optionally having halogen or polarizing or S—O Tridentates, water-insolubilizing/solubilizing groups S—O Tetradentates) attached. Ligand can also contain nonbinding N, O, S, or P atoms. Note: these ligands are not to be confused with hypophosphorous acid derivatives (hypophosphites) (R— O—)R″R″′P(═O) which are very reducing and therefore unacceptable for stabilization of high valence states in metal ions. S—O Valence (RR′—N—)(R″R′″—N—)P(═S)(—N— Stabilizer #6: R″″R″″′)(—N—R″″″R″″″′), where R, R′, Monothiohypo- R″, R″′, R″″, R″″′, R″″″, and R″″″′ represent phosphoramides, H, NH2 or any organic functional group Bis(monothiohypo- wherein the number of carbon atoms ranges phosphoramides), and from 0 to 40, optionally having halogen or Poly(monothiohypo- polarizing or water-insolubilizing/ phosphoramides) (S—O solubilizing groups attached. Ligand can also Bidentates, S—O contain nonbinding N, O, S, or P atoms. Tridentates, S—O Note: these ligands are not to be confused Tetradentates) with hypophosphorous acid derivatives (hypophosphites) (R—O—) R″R″′P(═O) which are very reducing and therefore unacceptable for stabilization of high valence states in metal ions. S—O Valence (R—O—)(R′—O—)P(═S)—NH— Stabilizer #7: P(═O)(—O—R″)(—O—R″′); Monothioimido- (R—O—)(R′—S—)P(S)—NH— diphosphoric Acids, P(═O)(—S—R″)(—0—R″′); or Monothiohydrazido- (R—S—)(R ′—S—)P(═S)—NH— diphosphoric Acids, P(═O)(—S—R″)(—S—R″′) Bis(monothioimido- for monothioimidodiphosphoric acids, diphosphoric Acids), and —NH—NH— derivatives for Bis(monothiohydrazido- monothiohydrazidodiphosphoric acids, where diphosphoric Acids), R,R′,R″, and R″′ represent H, NH2 or any Poly(monothioimidodi- organic functional group wherein the number phosphoric Acid), of carbon atoms ranges from 0 to 40, Poly(monothiohydrazido- optionally having halogen or polarizing or diphosphoric Acids), water-insolubilizing/solubilizing groups and derivatives thereof attached. Ligand can also contain nonbinding (5—O Bidentates, N, O, S, or P atoms. S—O Tridentates, S—O Tetradentates) S—O Valence (RR′—N—)(R″R″′—N—)P(═S)—NH— Stabilizer #8: P(═O)(—N—R″″R″″′)(—N—R″″″R″″″′) Monothioimidodi- for monothiolmidodiphosphoramides, and phosphoramides, —NH—NH— derivatives for Monothiohydrazidodi- monothiohydrazidodiphosphoramides, where phosphoramides, R, R′, R″, R″′, R″″, R″″′, R″″″, and R′″″″ Bis(monothioimidodi- represent H, NH2 or any organic functional phosphoramides), group wherein the number of carbon atoms Bis(monothiohydrazido- ranges from 0 to 40, optionally having diphosphoramides), halogen or polarizing or water- Poly(monothioimidodi- insolubilizing/solubilizing groups attached. phosphoramides), and Ligand can also contain nonbinding N, O, S, Poly(monothiohydrazido- or P atoms. diphosphoramides) (5—O Bidentates, 5—O Tridentates, 5—O Tetradentates) S—O Valence (RR′—N—)(R″R″′—N—)P(═S)—S— Stabilizer #9: P(═O)(—N—R″″R″″′)(—N—R″″″R″″″′), Monothiodi- or (RR ′—N—)(R″R″′—N—)P(═S)—O— phosphoramides, P(═O)(—N—R″″R″″′)(—N—R″″″R″″″′), Bis(monothioiphos- where R, R′, R″, R″′, R″″, R″″′, R″″″, phoramides), and and R″″″′ represent H, NH2 or any organic Poly(monothiodi- functional group wherein the number of phosphoramides) (S—O carbon atoms ranges from 0 to 40, optionally Bidentates, S—O having halogen or polarizing or water- Tridentates, S—O insolubilizing/solubilizing groups attached. Tetradentates) Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence (R—O—)(R′—O—)P(═S)—O— Stabilizer #10: P(═O)(—O—R″)(—O—R′″); Monothiodi- (R—O—)(R′—O—)P(═S)— phosphoric Acids, S—P(═O)(—O—R″)(—O—R′″); Bis(monothioi- (R—O—)(R′—O—)P(═S)— phosphoric Acids), O—P(═O)(—O—R″)(—O—R′″); Poly(monothiodi- (R—O—)(R′—O—)P(═S)— phosphoric Acids), and S—P(═O)(—O—R″)(—O—R′″); or derivatives thereof (R—S—)(R′—S—)P(═S)— (S—O Bidentates, S—P(═O)(—S—R″)(—S—R′″), S—O Tridentates, where R, R′, R″, R″′, R″″, R″″′, R″″″, and S—O Tetradentates) R″″″′ represent H, NH2 or any organic functional group wherein the number of carbon atoms ranges from 0 to 40, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence RR′N+═C(OH)(SH), where R and R′ Stabilizer #11: represent H, OH, SH, OR″ (R″═C1-C30 Monothiocarbamates, alkyl or aryl), SR″ (R″═C1-C30 alkyl Bis(monothio- or aryl), NH2 or any organic functional group carbamates), and wherein the number of carbon atoms ranges Poly(monothiocarbamates) from 0 to 40, optionally having halogen (including N- or polarizing or water-insolubilizing/ hydroxymonothio- solubilizing groups attached. Ligand carbamates and N- can also contain nonbinding N, O, S, mercaptomonothio- or P atoms. carbamates) (S—O Bidentates, S—O Tridentates, and S—O Tetradentates) Miscellaneous Valence Hydroxo and oxo ligands bound directly to Stabilizer #1: the high valence metal ion. Hydroxo and Oxo Ligands
[0112] N Valence Stabilizer #1: Examples of monoamines (N monodentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: ammonia; ethylamine; n-dodecylamine; octylamine; phenylamine; cyclohexylamine; diethylamine; dioctylamine; diphenylamine; dicyclohexylamine; azetidine; hexamethylenetetramine (Urotropin); aziridine; azepine; pyrrolidine; benzopyrrolidine; dibenzopyrrolidine; naphthopyrrolidine; piperidine; benzopiperidine; dibenzopiperidine; naphthopiperidine; azacycloheptane (hexamethyleneimine); aminonorbornane; adamantanamine; aniline; benzylamine; toluidine; phenethylamine; xylidine; cumidine; naphthylamine; polyalkylamines; polyanilines; and fluorenediamine.
[0113] N Valence Stabilizer #2: Examples of diamines (N—N bidentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: hydrazine; phenylhydrazine; 1,1-diphenylhydrazine; 1,2-diphenylhydrazine (hydrazobenzene); methanediamine; ethylenediamine (1,2-ethanediamine, en); trimethylenediamine (1,3-propanediamine); putrescine (1,4-butanediamine); cadaverine (1,5-pentanediamine); hexamethylenediamine (1,6-hexanediamine); 2,3-diaminobutane; stilbenediamine (1,2-diphenyl-1,2-ethanediamine); cyclohexane-1,2-diamine; cyclopentane-1,2-diamine; 1,3-diazacyclopentane; 1,3-diazacyclohexane; piperazine; benzopiperazine; dibenzopiperazine; naphthopiperazine; diazepine; thiadiazepine; oxodiazepine; sparteine (lupinidine); 2-(aminomethyl)azacyclohexane; 2-(aminomethyl)piperidine; 2-(aminomethyl)pyrrolidine; 2-(aminomethyl)azetidine; 2-(2-aminoethyl)aziridine; 1,2-diaminobenzene; benzidine; bis(2,2′-piperazino)-1,2-ethene; 1,4-diazabicyclo[2.2.2]octane; naphthylethylenediamine; and 1,2-dianilinoethane.
[0114] N Valence Stabilizer #3: Examples of triamines (N—N bidentates or N—N tridentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N-(2-aminoethyl)-1,2-ethanediamine (dien, 2,2-tri); N-(2-aminoethyl)-1,3-propanediamine (2,3-tri); N-(3aminopropyl)-1,3-propanediamine (3,3-tri, dpt); N-(3-aminopropyl)-1,4-butanediamine (3,4-tri, spermidine); N-(2-aminoethyl)-1,4-butanediamine (2,4-tri); N-(6-hexyl)-1,6-hexanediamine (6,6-tri); 1,3,5-triaminocyclohexane (tach); 2-(aminomethyl)-1,3-propanediamine (tamm); 2-(aminomethyl)-2-methyl-1,3-propanediamine (tame); 2-(aminomethyl)-2-ethyl-1,3-propanediamine (tamp); 1,2,3-triaminopropane (tap); 2,3-(2-aminoethyl)aziridine; 2,4-(aminomethyl)azetidine; 2,5-(aminomethyl)pyrrolidine; 2,6-(aminomethyl)piperidine; di(2-aminobenzyl)amine; hexahydro-1,3,5-triazine; hexahydro-2,4,6-trimethyl-1,3,5-triazine; and 1,3,5-tris(aminomethyl)benzene.
[0115] N Valence Stabilizer #4: Examples of tetramines (N—N bidentates, N—N tridentates, or N—N tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N,N′-(2-aminoethyl)-1,2-ethanediamine (2,2,2-tet, trien (triethylenetetramine)); N,N′-(2-aminoethyl)-1,3-propanediamine (2,3,2-tet, entnen); N,N′-(3-aminopropyl)-1,2-ethanediamine (3,2,3-tet, tnentn); N-(2-aminoethyl)-N′-(3-aminopropyl)-1,2-ethanediamine (2,2,3-tet); N-(2-aminoethyl)-N′-(3-aminopropyl)-1,3-propanediamine (3,3,2-tet); N,N′-(3-aminopropyl)-1,3-propanediamine (3,3,3-tet); N,N′-(3-aminopropyl)-1,4-butanediamine (3,4,3-tet, spermine); tri(aminomethyl)amine (tren); tri(2-aminoethyl)amine (trtn); tri(3-aminopropyl)amine (trbn); 2,2-aminomethyl-1,3-propanediamine (tam); 1,2,3,4-tetraminobutane (tab); N,N′-(2-aminophenyl)-1,2-ethanediamine; and N,N′-(2-aminophenyl)-1,3-propanediamine.
[0116] N Valence Stabilizer #5: Examples of pentamines (N—N bidentates, N—N tridentates, or N—N tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N-[N-(2-aminoethyl)-2-aminoethyl]-N′-(2-aminoethyl)-1,2-ethanediamine (2,2,2,2-pent, tetren); N-[N-(3-aminopropyl)-2-aminoethyl]-N′-(3-aminopropyl)-1,2-ethanediamine (3,2,2,3-pent); N-[N-(3-aminopropyl)-3-aminopropyl]-N ′-(3-aminopropyl)-1,3-propanediamine (3,3,3,3-pent, caldopentamine); N-[N-(2-aminobenzyl)-2-aminoethyl]-N′-(2-aminopropyl)-1,2-ethanediamine; N-[N-(2-aminoethyl)-2-aminoethyl]-N,N-(2-aminoethyl)amine (trenen); and N-[N-(2-aminopropyl)-2-aminoethyl]-N,N-(2-aminoethyl)amine (4-Me-trenen).
[0117] N Valence Stabilizer #6: Examples of hexamines (N—N bidentates, N—N tridentates, N—N tetradentates, or N—N—N—N—N—N hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N,N′-[N-(2-aminoethyl)-2-aminoethyl]-1,2-ethanediamine (2,2,2,2,2-hex, linpen); N,N′-[N-(2-aminoethyl)-3-aminopropyl]-1,2-ethanediamine (2,3,2,3,2-hex); N,N,N′,N′-(2-aminoethyl)-1,2-ethanediamine (penten, ten); N,N,N′,N′-(2-aminoethyl)-1-methyl-1,2-ethanediamine (tpn, R-5-Me-penten); N,N,N′,N′-(2-aminoethyl)-1,3-propanediamine (ttn); N,N,N′,N′-(2-aminoethyl)-1,4-butanediamine (tbn); N,N,N′,N′-(2-aminoethyl)-1,3-dimethyl-1,3-propanediamine (R,R-tptn, R,S-tptn); N-(2-aminoethyl)-2,2-[N-(2-aminoethyl)aminomethyl-1-propaneamine (sen); and N-(3-aminopropyl)-2,2-[N-(3-aminopropyl)aminomethyl-1-propaneamine (stn).
[0118] N Valence Stabilizer #7a: Examples of 5-membered heterocyclic rings containing one nitrogen atom (N monodentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 1-pyrroline, 2-pyrroline, 3-pyrroline, pyrrole, oxazole, isoxazole, thiazole, isothiazole, azaphosphole, benzopyrroline, benzopyrrole (indole), benzoxazole, benzisoxazole, benzothiazole, benzisothiazole, benzazaphosphole, dibenzopyrroline, dibenzopyrrole (carbazole), dibenzoxazole, dibenzisoxazole, dibenzothiazole, dibenzisothiazole, naphthopyrroline, naphthopyrrole, naphthoxazole, naphthisoxazole, naphthothiazole, naphthisothiazole, naphthazaphosphole, and polypyrroles.
[0119] N Valence Stabilizer #7b: Examples of 5-membered heterocyclic rings containing two nitrogen atoms (N monodentates or N—N bidentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: pyrazoline, imidazoline, imidazole (ia), pyrazole, oxadiazole, thiadiazole, diazaphosphole, benzopyrazoline, benzimidazoline, benzimidazole (azindole)(bia)(bz), benzopyrazole (indazole), benzothiadiazole (piazthiole), benzoxadiazole (benzofurazan), naphthopyrazoline, naphthimidazoline, naphthimidazole, naphthopyrazole, naphthoxadiazole, naphthothiadiazole, polybenzimidazole, and polyimidazoles (e.g. polyvinylimidazole (pvi)).
[0120] N Valence Stabilizer #7c: Examples of 5-membered heterocyclic rings containing three nitrogen atoms (N monodentates, N—N bidentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: triazole, oxatriazole, thiatriazole, benzotriazole (bta), tolyltriazole (tt), naphthotriazole, and triazolophthalazine.
[0121] N Valence Stabilizer #7d: Examples of 5-membered heterocyclic rings containing four nitrogen atoms (N monodentates or N—N bidentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: tetrazole.
[0122] N Valence Stabilizer #8a: Examples of 6-membered heterocyclic rings containing one nitrogen atom (N monodentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: pyridine, picoline, lutidine, &ggr;-collidine, oxazine, thiazine, azaphosphorin, quinoline, isoquinoline, benzoxazine, benzothiazine, benzazaphosphorin, acridine, phenanthridine, phenothiazine (dibenzothiazine), dibenzoxazine, dibenzazaphosphorin, benzoquinoline (naphthopyridine), naphthoxazine, naphthothiazine, naphthazaphosphorin, and polypyridines.
[0123] N Valence Stabilizer #8b: Examples of 6-membered heterocyclic rings containing two nitrogen atoms (N monodentates or N—N bidentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: pyrazine, pyridazine, pyrimidine, oxadiazine, thiadiazine, diazaphosphorin, quinoxaline (benzopyrazine), cinnoline (benzo[c]pyridazine), quinazoline (benzopyrimidine), phthalazine (benzo[d]pyridazine), benzoxadiazine, benzothiadiazine, phenazine (dibenzopyrazine), dibenzopyridazine, naphthopyrazine, naphthopyridazine, naphthopyrimidine, naphthoxadiazine, naphthothiadiazine, and polyquinoxalines.
[0124] N Valence Stabilizer #8c: Examples of 6-membered heterocyclic rings containing three nitrogen atoms (N monodentates or N—N bidentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 1,3,5-triazine, 1,2,3-triazine, benzo-1,2,3-triazine, naphtho-1,2,3-triazine, oxatriazine, thiatriazine, melamine, and cyanuric acid.
[0125] N Valence Stabilizer #8d: Examples of 6-membered heterocyclic rings containing four nitrogen atoms (N monodentates or N—N bidentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: tetrazine.
[0126] N Valence Stabilizer #9a: Examples of 5-membered heterocyclic rings containing one nitrogen atom and having at least one additional nitrogen atom binding site not contained in a ring (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-(aminomethyl)-3-pyrroline; 2,5-(aminomethyl)-3-pyrroline; 2-(aminomethyl)pyrrole; 2,5-(aminomethyl)pyrrole; 3-(aminomethyl)isoxazole; 2-(aminomethyl)thiazole; 3-(aminomethyl)isothiazole; 2-(aminomethyl)indole; 2-aminobenzoxazole; 2-aininobenzothiazole (abt); 1,8-diaminocarbazole; 2-amino-6-methyl-benzothiazole (amebt); 2-amino-6-methoxybenzothiazole (ameobt), and 1,3-diiminoisoindoline.
[0127] N Valence Stabilizer #9b: Examples of 5-membered heterocyclic rings containing two nitrogen atoms at least one additional nitrogen atom binding site not contained in a ring (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-aminoimidazoline; 1-(3-aminopropyl)imidazoline; 2-aminoimidazole; 1-(3-aminopropyl)imidazole; 4-(2-aminoethyl)imidazole [histamine]; 1-alkyl-4-(2-aminoethyl)imidazole; 3-(2-aminoethyl)pyrazole; 3,5-(2-aminoethyl)pyrazole; 1-(aminomethyl)pyrazole; 2-aminobenzimidazole; 7-(2-aminoethyl)benzimidazole; 1-(3-aminopropyl)benzimidazole; 3-(2-aminoethyl)indazole; 3,7-(2-aminoethyl)indazole; 1-(aminomethyl)indazole; 7-aminobenzothiadiazole; 4-(2-aminoethyl)benzothiadiazole; 7-aminobenzoxadiazole; 4-(2-aminoethyl)benzoxadiazole; ethylenediaminetetra(1-pyrazolylmethane) [edtp]; methylenenitrilotris(2-(1-methyl)benzimidazole) [mntb] [tris(1-methyl-2-benzimidazolylmethane)amine]; bis(alkyl-1-pyrazolylmethane)amine; bis(alkyl-2-(1-pyrazolyl)ethane)amine; bis(N,N-(2-benzimidazolyl)-2-aminoethane)(2-benzimidazolylmethane)amine; bis(1-(3,5-dimethyl)pyrazolylmethane)phenylamine; tris(2-(1-(3,5-dimethyl)pyrazolyl)ethane)amine; 5-(dimethylamino)pyrazole; 5-(dimethylaminomethyl)pyrazole; 2-amino-1,3,4-thiadiazole; and 1-(2-aminoethyl)imidazoline.
[0128] N Valence Stabilizer #9c: Examples of 5-membered heterocyclic rings containing three nitrogen atoms at least one additional nitrogen atom binding site not contained in a ring (N Monodentates, N—N Bidentates, N—N—N Tridentates, N—N—N—N Tetradentates, or N—N—N—N—N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 3-amino-1,2,4-triazole (ata); 3,5-diamino-1,2,4-triazole (dat); 5-amino-1,2,4-triazole; 3-(2-aminoethyl)-1,2,4-triazole; 5-(2-aminoethyl)-1,2,4-triazole; 3,5-(2-aminoethyl)-1,2,4-triazole; 1-(aminomethyl)-1,2,4-triazole; 3,5-(aminomethyl)-4-amino-1,2,4-triazole; 4-(2-aminoethyl)-1,2,3-triazole; 5-(2-aminoethyl)-1,2,3-triazole; 7-aminobenzotriazole; 1-(aminomethyl)-1,2,3-triazole; 1-(2-aminoethyl)-1,2,3-triazole; 4-(3-aminopropyl)benzotriazole; N-(benzotriazolylalkyl)amine; dibenzotriazole-1-ylalkylamine; bis(5-amino-1,2,4-triazol-3-yl); bis(5-amino-1,2,4-triazol-3-yl)alkanes; and 1-(aminomethyl)benzotriazole.
[0129] N Valence Stabilizer #9d: Examples of 5-membered heterocyclic rings containing four nitrogen atoms at least one additional nitrogen atom binding site not contained in a ring (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 5-(2-aminoethyl)-1H-tetrazole; 1-(aminomethyl)-1H-tetrazole; and 1-(2-aminoethyl)-1H-tetrazole.
[0130] N Valence Stabilizer #10a: Examples of 6-membered heterocyclic rings containing one nitrogen atom and having at least one additional nitrogen atom binding site not contained in a ring (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-aminopyridine; 2,6-diaminopyridine; 2-(aminomethyl)pyridine; 2,6-(aminomethyl)pyridine; 2,6-(aminoethyl)pyridine; 2-amino-4-picoline; 2,6-diamino-4-picoline; 2-amino-3,5-lutidine; 2-aminoquinoline; 8-aminoquinoline; 2-aminoisoquinoline; acriflavine; 4-aminophenanthridine; 4,5-(aminomethyl)phenothiazine; 4,5-(aminomethyl)dibenzoxazine; 10-amino-7,8-benzoquinoline; bis(2-pyridylmethane)amine; tris(2-pyridyl)amine; bis(4(2-pyridyl)-3-azabutane)amine; bis(N,N-(2-(2-pyridyl)ethane)aminomethane)amine; 4-(N,N-dialkylaminomethyl)morpholine; 6-aminonicotinic acid; 8-aminoacridine; and 2-hydrazinopyridine.
[0131] N Valence Stabilizer #10b: Examples of 6-membered heterocyclic rings containing two nitrogen atoms at least one additional nitrogen atom binding site not contained in a ring (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-aminopyrazine; 2,6-diaminopyrazine; 2-(aminomethyl)pyrazine; 2,6-(aminomethyl)pyrazine; 3-(aminomethyl)pyridazine; 3,6-(aminomethyl)pyridazine; 3,6-(2-aminoethyl)pyridazine; 1-aminopyridazine; 1-(aminomethyl)pyridazine; 2-aminopyrimidine; 1-(2-aminoethyl)pyrimidine; 2-aminoquinoxaline; 2,3-diaminoquinoxaline; 2-aminocinnoline; 3-aminocinnoline; 3-(2-aminoethyl)cinnoline; 3,8-(2-aminoethyl)cinnoline; 2-aminoquinazoline; 1-(2-aminoethyl)quinazoline; 1-aminophthalazine; 1,4-(2-aminoethyl)phthalazine; 1,8-(aminomethyl)phenazine; 2-amino-4,6-dimethylpyrimidine (admp); dihydralazine; and hydralazine.
[0132] N Valence Stabilizer #10c: Examples of 6-membered heterocyclic rings containing three nitrogen atoms at least one additional nitrogen atom binding site not contained in a ring (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-amino-1,3,5-triazine; 2-(aminomethyl)-1,3,5-triazine; 2,6-(aminomethyl)-1,3,5-triazine; 1-(3-aminopropyl)-1,3,5-triazine; 1,5-(3-aminopropyl)-1,3,5-triazine, polymelamines; melamine; and altretamine.
[0133] N Valence Stabilizer #10d: Examples of 6-membered heterocyclic rings containing four nitrogen atoms at least one additional nitrogen atom binding site not contained in a ring (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 3,6-(2-aminoethyl)-1,2,4,5-tetrazine; 3,6-(1,3-diamino-2-propyl)-1,2,4,5-tetrazine; and 4,6-(aminomethyl)-1,2,3,5-tetrazine.
[0134] N Valence Stabilizer #11a: Examples of 5-membered heterocyclic rings containing one nitrogen atom and having at least one additional nitrogen atom binding site contained in a ring (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2,2′-bi-3-pyrroline; 2,2′-bi-2-pyrroline; 2,2′-bi-1-pyrroline; 2,2′-bipyrrole; 2,2′,2″-tripyrrole; 3,3′-biisoxazole; 2,2′-bioxazole; 3,3′-biisothiazole; 2,2′-bithiazole; 2,2′-biindole; 2,2′-bibenzoxazole; 2,2′-bibenzothiazole; bilirubin; biliverdine; and 7-azaindole.
[0135] N Valence Stabilizer #11b: Examples of 5-membered heterocyclic rings containing two nitrogen atoms at least one additional nitrogen atom binding site contained in a ring (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2,2′-bi-2-imidazoline [2,2′-bi-2-imidazolinyl][bimd]; 2,2′-biimidazole [2,2′-biimidazolyl][biimH2]; 5,5′-bipyrazole; 3,3′-bipyrazole; 4,4′-bipyrazole [4,4′-bipyrazolyl][bpz]; 2,2′-bioxadiazole; 2,2′-bithiadiazole; 2,2′-bibenzimidazole; 7,7′-biindazole; 5,5′-bibenzofurazan; 5,5′-bibenzothiadiazole; bis-1,2-(2=benzimidazole)ethane; bis(2-benzimidazole)methane; 1,2-(2-imidazolyl)benzene; 2-(2-thiazolyl)benzimidazole; 2-(2-imidazolyl)benzimidazole; benzimidazotriazine; 4-azabenzimidazole; and 2,6-bis(2-benzimidazolyl)pyridine.
[0136] N Valence Stabilizer #11c: Examples of 5-membered heterocyclic rings containing three nitrogen atoms at least one additional nitrogen atom binding site contained in a ring (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 5,5′-bi-1,2,4-triazole [btrz]; 3,3′-bi-1,2,4-triazole; 1,1′-bi-1,2,4-triazole; 1,1′-bi-1,2,3-triazole; 5,5′-bi-1,2,3-triazole; 7,7′-bibenzotriazole; 1,1′-bibenzotriazole; bis(pyridyl)aminotriazole (pat); and 8-azaadenine.
[0137] N Valence Stabilizer #11d: Examples of 5-membered heterocyclic rings containing four nitrogen atoms at least one additional nitrogen atom binding site contained in a ring (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 5,5′-bi-1H-tetrazole; and 1,1′-bi-1H-tetrazole.
[0138] N Valence Stabilizer #12a: Examples of 6-membered heterocyclic rings containing one nitrogen atom and having at least one additional nitrogen atom binding site contained in a ring (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2,2′-bipyridine [bipy]; 2,2′,2″-tripyridine [terpyridine] [terpy]; 2,2′,2″,2′″-tetrapyridine [tetrapy]; 6,6′-bi-2-picoline; 6,6′-bi-3-picoline; 6,6′-bi-4-picoline; 6,6′-bi-2,3-lutidine; 6,6′-bi-2,4-lutidine; 6,6′-bi-3,4-lutidine; 6,6′-bi-2,3,4-collidine; 2,2′-biquinoline; 2,2′-biisoquinoline; 3,3′-bibenzoxazine; 3,3′-bibenzothiazine; 1,10-phenanthroline [phen]; 1,8-naphthyridine; bis-1,2-(6-(2,2′-bipyridyl))ethane; bis-1,3-(6-(2,2′-bipyridyl))propane; 3,5-bis(3-pyridyl)pyrazole; 3,5-bis(2-pyridyl)triazole; 1,3-bis(2-pyridyl)-1,3,5-triazine; 1,3-bis(2-pyridyl)-5-(3-pyridyl)-1,3,5-triazine; 2,7-(N,N′-di-2-pyridyl)diaminobenzopyiroline; 2,7-(N,N′-di-2-pyridyl)diaminophthalazine; 2,6-di-(2-benzothiazolyl)pyridine; triazolopyrimidine; 2-(2-pyridyl)imidazoline; 7-azaindole; i-(2-pyridyl)pyrazole; (1-imidazolyl)(2-pyridyl)methane; 4,5-bis(N,N′-(2-(2-pyridyl)ethyl)iminomethyl)imidazole; bathophenanthroline; 4-(2-benzimidazolyl)quinoline; 1,2-bis(2-pyridyl)ethane; 4,4′-diphenyl-2,2′-dipyridyl; neocuproine; nicotine; and nornicotine.
[0139] N Valence Stabilizer #12b: Examples of 6-membered heterocyclic rings containing two nitrogen atoms at least one additional nitrogen atom binding site contained in a ring (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2,2′-bipyrazine; 2,2′,2″-tripyrazine; 6,6′-bipyridazine; bis(3-pyridazinyl)methane; 1,2-bis(3-pyridazinyl)ethane; 2,2′-bipyrimidine; 2,2′-biquinoxaline; 8,8′-biquinoxaline; bis(3-cinnolinyl)methane; bis(3-cinnolinyl)ethane; 8,8′-bicinnoline; 2,2′-biquinazoline; 4,4′-biquinazoline; 8,8′-biquinazoline; 2,2′-biphthalazine; 1,1′-biphthalazine; 2-(2-pyridyl)benzimidazole; 8-azapurine; purine; adenine; guanine; hypoxanthine; 2,6-bis(N,N′-(2-(4-imidazolyl)ethyl)iminomethyl)pyridine; 2-(N-(2-(4-imidazolyl)ethyl)iminomethyl)pyridine; adenine (aminopurine); purine; and 2,3-bis(2-pyridyl)pyrazine.
[0140] N Valence Stabilizer #12c: Examples of 6-membered heterocyclic rings containing three nitrogen atoms at least one additional nitrogen atom binding site contained in a ring (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2,2′-bi-1,3,5-triazine; 2,2′,2″-tri-1,3,5-triazine; 4,4′-bi-1,2,3-triazine; and 4,4′-bibenzo-1,2,3-triazine; 2,4,6-tris(2-pyridyl)-1,3,5-triazine; and benzimidazotriazines.
[0141] N Valence Stabilizer #12d: Examples of 6-membered heterocyclic rings containing four nitrogen atoms at least one additional nitrogen atom binding site contained in a ring (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 3,3′-bi-1,2,4,5-tetrazine; and 4,4′-bi-1,2,3,5-tetrazine.
[0142] N Valence Stabilizer #13a: Examples of two-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein both binding sites are composed of nitrogen (usually amine or imine groups) and are not contained in component heterocyclic rings (N—N Bidentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diazacyclobutane ([4]aneN2); diazacyclopentane ([5]aneN2); diazacyclohexane ([6]aneN2); diazacycloheptane ([7]aneN2); diazacyclooctane ([8]aneN2); piperazine; benzopiperazine; diazacyclobutene ([4]eneN2); diazacyclopentene ([5]eneN2); diazacyclohexene ([6]eneN2); diazacycloheptene ([7]eneN2); diazacyclooctene ([8]eneN2); diazacyclobutadiene ([4]dieneN2); diazacyclopentadiene ([5]dieneN2); diazacyclohexadiene ([6]dieneN2); diazacycloheptadiene ([7]dieneN2); and diazacyclooctadiene ([8]dieneN2).
[0143] N Valence Stabilizer #13b: Examples of three-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen (usually amine or imine groups) and are not contained in component heterocyclic rings (N—N Tridentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: triazacyclohexane (including hexahydro-1,3,5-triazine)([6]aneN3); triazacycloheptane ([7]aneN3); triazacyclooctane ([8]aneN3); triazacyclononane ([9]aneN3); triazacyclodecane ([10]aneN3); triazacycloundecane ([11]aneN3); triazacyclododecane ([12]aneN3); triazacyclohexene ([6]eneN3); triazacycloheptene ([7]eneN3); triazacyclooctene ([8]eneN3); triazacyclononene ([9]eneN3); triazacyclodecene ([10]eneN3); triazacycloundecene ([11]eneN3); triazacyclododecene ([12]eneN3); triazacyclohexatriene ([6]trieneN3); triazacycloheptatriene ([7]trieneN3); triazacyclooctatriene ([8]trieneN3); triazacyclononatriene ([9]trieneN3); triazacyclodecatriene ([10]trieneN3); triazacycloundecatriene ([11]trieneN3); and triazacyclododecatriene ([12]trieneN3).
[0144] N Valence Stabilizer #13c: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen (usually amine or imine groups) and are not contained in component heterocyclic rings (N—N Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: tetraazacyclooctane ([8]aneN4); tetraazacyclononane ([9]aneN4); tetraazacyclodecane ([10]aneN4); tetraazacycloundecane ([11]aneN4); tetraazacyclododecane ([12]aneN4); tetraazacyclotridecane ([13]aneN4); tetraazacyclotetradecane ([14]aneN4); tetraazacyclopentadecane ([15]aneN4); tetraazacyclohexadecane ([16]aneN4); tetraazacycloheptadecane ([17]aneN4); tetraazacyclooctadecane ([18]aneN4); tetraazacyclononadecane ([19]aneN4); tetraazacycloeicosane ([20]aneN4); tetraazacyclooctadiene ([8]dieneN4); tetraazacyclononadiene ([9]dieneN4); tetraazacyclodecadiene ([10]dieneN4); tetraazacycloundecadiene ([11]dieneN4); tetraazacyclododecadiene ([12]dieneN4); tetraazacyclotridecadiene ([13]dieneN4); tetraazacyclotetradecadiene ([14]dieneN4); tetraazacyclopentadecadiene ([15]dieneN4); tetraazacyclohexadecadiene ([16]dieneN4); tetraazacycloheptadecadiene ([17]dieneN4); tetraazacyclooctadecadiene ([18]dieneN4); tetraazacyclononadecadiene ([19]dieneN4); tetraazacycloeicosadiene ([20]dieneN4); tetraazacyclooctatetradiene ([8]tetradieneN4); tetraazacyclononatetradiene ([9]tetradieneN4); tetraazacyclodecatetradiene ([10]tetradieneN4); tetraazacycloundecatetradiene ([11]tetradieneN4); tetraazacyclododecatetradiene ([12]tetradieneN4); tetraazacyclotridecatetradiene ([13]tetradieneN4); tetraazacyclotetradecatetradiene ([14]tetradieneN4); tetraazacyclopentadecatetradiene ([15]tetradieneN4); tetraazacyclohexadecatetradiene ([16]tetradieneN4); tetraazacycloheptadecatetradiene ([17]tetradieneN4); tetraazacyclooctadecatetradiene ([18]tetradieneN4); tetraazacyclononadecatetradiene ([19]tetradieneN4); and tetraazacycloeicosatetradiene ([20]tetradieneN4).
[0145] N Valence Stabilizer #13d: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen (usually amine or imine groups) and are not contained in component heterocyclic rings (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: hexaazacyclododecane ([12]aneN6); hexaazacyclotridecane ([13]aneN6); hexaazacyclotetradecane ([14]aneN6); hexaazacyclopentadecane ([15]aneN6); hexaazacyclohexadecane ([16]aneN6); hexaazacycloheptadecane ([17]aneN6); hexaazacyclooctadecane ([18]aneN6); hexaazacyclononadecane ([19]aneN6); hexaazacycloeicosane ([20]aneN6); hexaazacycloheneicosane ([21]aneN6); hexaazacyclodocosane ([22]aneN6); hexaazacyclotricosane ([23]aneN6); hexaazacyclotetracosane ([24]aneN6); hexaazacyclododecatriene ([12]trieneN6); hexaazacyclotridecatriene ([13]trieneN6); hexaazacyclotetradecatriene ([14]trieneN6); hexaazacyclopentadecatriene ([15]trieneN6); hexaazacyclohexadecatriene ([16]trieneN6); hexaazacycloheptadecatriene ([17]trieneN6); hexaazacyclooctadecatriene ([18]trieneN6); hexaazacyclononadecatriene ([19]trieneN6); hexaazacycloeicosatriene ([20]trieneN6); hexaazacycloheneicosatriene ([21]trieneN6); hexaazacyclodocosatriene ([22]trieneN6); hexaazacyclotricosatriene ([23]trieneN6); and hexaazacyclotetracosatriene ([24]trieneN6).
[0146] N Valence Stabilizer #13e: Examples of eight-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen (usually amine or imine groups) and are not contained in component heterocyclic rings (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: octaazacyclohexadecane ([16]aneN8); octaazacycloheptadecane ([17]aneN8); octaazacyclooctadecane ([18]aneN8); octaazacyclononadecane ([19]aneN8); octaazacycloeicosane ([20]aneN8); octaazacycloheneicosane ([21]aneN8); octaazacyclodocosane ([22]aneN8); octaazacyclotricosane ([23]aneN8); octaazacyclotetracosane ([24]aneN8); octaazacyclohexadecatetradiene ([16]tetradieneN8); octaazacycloheptadecatetradiene ([17]tetradieneN8); octaazacyclooctadecatetradiene ([18]tetradieneN8); octaazacyclononadecatetradiene ([19]tetradieneN8); octaazacycloeicosatetradiene ([20]tetradieneN8); octaazacycloheneicosatetradiene ([21]tetradieneN8); octaazacyclodocosatetradiene ([22]tetradieneN8); octaazacyclotricosatetradiene ([23]tetradieneN8); and octaazacyclotetracosatetradiene ([24]tetradieneN8).
[0147] N Valence Stabilizer #13f: Examples of ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchratcs) wherein all binding sites are composed of nitrogen (usually amine or imine groups) and are not contained in component heterocyclic rings (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: decaazacycloeicosane ([20]aneN0); decaazacycloheneicosane ([21]aneN10); decaazacyclodocosane ([22]aneN10); decaazacyclotricosane ([23]aneN10); decaazacyclotetracosane ([24]aneN10); decaazacyclopentacosane ([25]aneN10); decaazacyclohexacosanc ([26]aneN10); decaazacycloheptacosane ([27]aneN10); decaazacyclooctacosane ([28]aneN10); decaazacyclononacosane ([29]aneN10); decaazacyclotriacontane ([30]aneN10); decaazacycloeicosapentadiene ([20]pentadieneN10); decaazacycloheneicosapentadiene ([21]pentadieneN10); decaazacyclodocosapentadiene ([22]pentadieneN10); decaazacyclotricosapentadiene ([23]pentadieneN10); decaazacyclotetracosapentadiene ([24]pentadieneN10); decaazacyclopentacosapentadiene ([25]pentadieneN10); decaazacyclohexacosapentadiene ([26]pentadieneN10); decaazacycloheptacosapentadiene ([27]pentadieneN10); decaazacyclooctacosapentadiene ([28]pentadieneN10); decaazacyclononacosapentadiene ([29]pentadieneN10); and decaazacyclotriacontapentadiene ([30]pentadieneN10).
[0148] N Valence Stabilizer #14a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of nitrogen and are contained in component 5-membered heterocyclic rings (N—N Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: porphyrins (including tetraphenylporphine (tpp); “picket fence” porphyrins, “picket tail” porphyrins, “bispocket” porphyrins, “capped” porphyrins, cyclophane porphyrins, “pagoda” porphyrins, “pocket” porphyrins, “pocket tail” porphyrins, cofacial diporphyrins, “strapped” porphyrins, “hanging base” porphyrins, bridged porphyrins, chelated mesoporphyrins, homoporphyrins, chlorophylls, and pheophytins); porphodimethanes; porphyrinogens; chlorins; bacteriochlorins; isobacteriochlorins; corroles; corrins and corrinoids; didehydrocorrins; tetradehydrocorrins; hexadehydrocorrins; octadehydrocorrins; tetraoxazoles; tetraisooxazoles; tetrathiazoles; tetraisothiazoles; tetraazaphospholes; tetraimidazoles; tetrapyrazoles; tetraoxadiazoles; tetrathiadiazoles; tetradiazaphospholes; tetratriazoles; tetraoxatriazoles; tetrathiatriazoles; coproporphyrin; etioporphyrin; and hematoporphyrin.
[0149] N Valence Stabilizer #14b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of nitrogen and are contained in component 5-membered heterocyclic rings (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: hexaphyrins (hexapyrroles); hexaoxazoles; hexaisooxazoles; hexathiazoles; hexaisothiazoles; hexaazaphospholes; hexaimidazoles; hexapyrazoles; hexaoxadiazoles; hexathiadiazoles; hexadiazaphospholes; hexatriazoles; hexaoxatriazoles; and hexathiatriazoles.
[0150] N Valence Stabilizer #14c: Examples of eight-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all eight binding sites are composed of nitrogen and are contained in component 5-membered heterocyclic rings (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: octaphyrins (octapyrroles); octaoxazoles; octaisooxazoles; octathiazoles; octaisothiazoles; octaazaphospholes; octaimidazoles; octapyrazoles; octaoxadiazoles; octathiadiazoles; octadiazaphospholes; octatriazoles; octaoxatriazoles; and octathiatriazoles.
[0151] N Valence Stabilizer #14d: Examples of ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all ten binding sites are composed of nitrogen and are contained in component 5-membered heterocyclic rings (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: decaphyrins (decapyrroles); decaoxazoles; decaisooxazoles; decathiazoles; decaisothiazoles; decaazaphospholes; decaimidazoles; decapyrazoles; decaoxadiazoles; decathiadiazoles; decadiazaphospholes; decatriazoles; decaoxatriazoles; and decathiatriazoles.
[0152] N Valence Stabilizer #15a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of nitrogen and are contained in a combination of 5-membered heterocyclic rings and amine or imine groups (N—N Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: porphyrazines; octahydrodiazaporphyrins; phthalocyanines; naphthalocyanines; anthracocyanines; and tetraazaporphyrins
[0153] N Valence Stabilizer #15b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of nitrogen and are contained in a combination of 5-membered heterocyclic rings and amine or imine groups (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diazahexaphyrins; tetraazahexaphyrins; hexaazahexaphyrins; diazahexapyrazoles; tetraazahexapyrazoles; hexaazahexapyrazoles; diazahexaimidazoles; tetraazahexaimidazoles; and hexaazahexaimidazoles.
[0154] N Valence Stabilizer #15c: Examples of eight-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all eight binding sites are composed of nitrogen and are contained in a combination of 5-membered heterocyclic rings and amine or imine groups (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diazaoctaphyrins; tetraazaoctaphyrins; hexaazaoctaphyrins; octaazaoctaphyrins; diazaoctapyrazoles; tetraazaoctapyrazoles; hexaazaoctapyrazoles; octaazaoctapyrazoles; diazaoctaimidazoles; tetraazaoctaimidazoles; hexaazaoctaimidazoles; and octaazaoctaimidazoles.
[0155] N Valence Stabilizer #15d: Examples of ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all ten binding sites are composed of nitrogen and are contained in a combination of 5-membered heterocyclic rings and amine or imine groups (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diazadecaphyrins; tetraazadecaphyrins; hexaazadecaphyrins; octaazadecaphyrins; decaazadecaphyrins; diazadecapyrazoles; tetraazadecapyrazoles; hexaazadecapyrazoles; octaazadecapyrazoles; decaazadecapyrazoles; diazadecaimidazoles; tetraazadecaimidazoles; hexaazadecaimidazoles; octaazadecaimidazoles; and decaazadecaimidazoles.
[0156] N Valence Stabilizer #16a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of nitrogen and are contained in component 6-membered heterocyclic rings (N—N Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: cyclotetrapyridines; cyclotetraoxazines; cyclotetrathiazines; cyclotetraphosphorins; cyclotetraquinolines; cyclotetrapyrazines; cyclotetrapyridazines; cyclotetrapyrimidines; cyclotetraoxadiazines; cyclotetrathiadiazines; cyclotetradiazaphosphorins; cyclotetraquinoxalines; cyclotetratriazines; cyclotetrathiatriazines; and cyclotetraoxatriazines.
[0157] N Valence Stabilizer #16b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of nitrogen and are contained in component 6-membered heterocyclic rings (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: cyclosexipyridines; cyclosexioxazines; cyclosexithiazines; cyclosexiphosphorins; cyclosexiquinolines; cyclosexipyrazines; cyclosexipyridazines; cyclosexipyrimidines; cyclosexioxadiazines; cyclosexithiadiazines; cyclosexidiazaphosphorins cyclosexiquinoxalines; cyclosexitriazines; cyclosexithiatriazines; and cyclosexioxatriazines.
[0158] N Valence Stabilizer #16c: Examples of eight-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of nitrogen and are contained in component 6-membered heterocyclic rings (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: cyclooctapyridines; cyclooctaoxazines; cyclooctathiazines; cyclooctaphosphorins; cyclooctaquinolines; cyclooctapyrazines; cyclooctapyridazines; cyclooctapyrimidines; cyclooctaoxadiazines; cyclooctathiadiazines; cyclooctadiazaphosphorins; cyclooctaquinoxalines; cyclooctatriazines; cyclooctathiatriazines; and cyclooctaoxatriazines.
[0159] N Valence Stabilizer #16d: Examples of ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of nitrogen and are contained in component 6-membered heterocyclic rings (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: cyclodecapyridines; cyclodecaoxazines; cyclodecathiazines; cyclodecaphosphorins; cyclodecaquinolines; cyclodecapyrazines; cyclodecapyridazines; cyclodecapyrimidines; cyclodecaoxadiazines; cyclodecathiadiazines; cyclodecadiazaphosphorins; cyclodecaquinoxalines; cyclodecatriazines; cyclodecathiatriazines; and cyclodecaoxatriazines.
[0160] N Valence Stabilizer #17a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of nitrogen and are contained in a combination of 6-membered heterocyclic rings and amine or imine groups (N—N Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diazacyclotetrapyridines; tetraazacyclotetrapyridines; diazacyclotetraquinolines; tetraazacyclotetraquinolines; diazacyclotetrapyrazines; tetraazacyclotetrapyrazines; diazacyclotetrapyridazines; tetraazacyclotetrapyridazines; diazacyclotetrapyrimidines; tetraazacyclotetrapyrimidines; diazacyclotetratriazines; and tetraazacyclotetratriazines.
[0161] N Valence Stabilizer #17b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of nitrogen and are contained in a combination of 6-membered heterocyclic rings and amine or imine groups (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diazacyclosexipyridines; triazacyclosexipyridines; diazacyclosexiquinolines; triazacyclosexiquinolines; diazacyclosexipyrazines; triazacyclosexipyrazines; diazacyclosexipyridazines; triazacyclosexipyridazines; diazacyclosexipyrimidines; triazacyclosexipyrimidines; diazacyclosexitriazines; and triazacyclosexitriazines.
[0162] N Valence Stabilizer #17c: Examples of eight-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all eight binding sites are composed of nitrogen and are contained in a combination of 6-membered heterocyclic rings and amine or imine groups (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diazacyclooctapyridines; tetraazacyclooctapyridines; diazacyclooctaquinolines; tetraazacyclooctaquinolines; diazacyclooctapyrazines; tetraazacyclooctapyrazines; diazacyclooctapyridazines; tetraazacyclooctapyridazines; diazacyclooctapyrimidines; tetraazacyclooctapyrimidines; diazacyclooctatriazines; and tetraazacyclooctatriazines.
[0163] N Valence Stabilizer #17d: Examples of ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all ten binding sites are composed of nitrogen and are contained in a combination of 6-membered heterocyclic rings and amine or imine groups (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diazacyclodecapyridines; pentaazacyclodecapyridines; diazacyclodecaquinolines; pentaazacyclodecaquinolines; diazacyclodecapyrazines; pentaazacyclodecapyrazines; diazacyclodecapyridazines; pentaazacyclodecapyridazines; diazacyclodecapyrimidines; pentaazacyclodecapyrimidines; diazacyclodecatriazines; and pentaazacyclodecatriazines.
[0164] N Valence Stabilizer #18: Examples of amidines and diamidines (N—N bidentates or N—N Tetradentates) that meet the requirements for use as ““wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N,N′-dimethylformamidine; N,N′-diethylformamidine; N,N′-diisopropylformamidine; N,N′-dibutylformamidine; N,N′-diphenylformamidine; N,N′-dibenzylformamidine; N,N′-dinaphthylformamidine; N,N′-dicyclohexylformamidine; N,N′-dinorbornylformamidine; N,N′-diadamantylformamidine; N,N′-dianthraquinonylformamidine; N,N′-dimethylacetamidine; N,N′-diethylacetamidine; N,N′-diisopropylacetamidine; N,N′-dibutylacetamidine; N,N′-diphenylacetamidine; N,N′-dibenzylacetamidine; N,N′-dinaphthylacetamidine; N,N′-dicyclohexylacetamidine; N,N′-dinorbornylacetamidine; N,N′-diadamantylacetamidine; N,N′-dimethylbenzamidine; N,N′-diethylbenzamidine; N,N′-diisopropylbenzamidine; N,N′-dibutylbenzamidine; N,N′-diphenylbenzamidine; N,N′-dibenzylbenzamidine; N,N′-dinaphthylbenzamidine; N,N′-dicyclohexylbenzamidine; N,N′-dinorbornylbenzamidine; N,N′-diadamantylbenzamidine; N,N′-dimethyltoluamidine; N,N′-diethyltoluamidine; N,N′-diisopropyltoluamidine; N,N′-dibutyltoluamidine; N,N′-diphenyltoluamidine; N,N′-dibenzyltoluamidine; N,N′-dinaphthyltoluamidine; N,N′-dicyclohexyltoluamidine; N,N′-dinorbornyltoluamidine; N,N′-diadamantyltoluamidine; oxalic diamidine; malonic diamidine; succinic diamidine; glutaric diamidine; adipic diamidine; pimelic diamidine; suberic diamidine; phthalic diamidine; terephthalic diamidine; isophthalic diamidine; piperazine diamidine; 2-iminopyrrolidine; 2-iminopiperidine; amidinobenzamide; benzamidine; chloroazodin; and debrisoquin.
[0165] N Valence Stabilizer #19: Examples of biguamides (imidodicarbonimidic diamides), biguanidines, imidotricarbonimidic diamides, imidotetracarbonimidic diamides, dibiguamides, bis(biguanidines), polybiguamides, and poly(biguanidines) (N—N bidentates, N—N tridentates, N—N tetradentates, and N—N hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: biguamide (bigH); biguanidine, methylbiguamide; ethylbiguamide; isopropylbiguamide; butylbiguamide; benzylbiguamide; phenylbiguamide; tolylbiguamide; naphthylbiguamide; cyclohexylbiguamide; norbornylbiguamide; adamantylbiguamide; dimethylbiguamide; diethylbiguamide; diisopropylbiguamide; dibutylbiguamide; dibenzylbiguamide; diphenylbiguamide; ditolylbiguamide; dinaphthylbiguamide; dicyclohexylbiguamide; dinorbornylbiguamide; diadamantylbiguamide; ethylenedibiguamide; propylenedibiguamide; tetramethylenedibiguamide; pentamethylenedibiguamide; hexamethylenedibiguamide; heptamethylenedibiguamide; octamethylenedibiguamide; phenylenedibiguamide; piperazinedibiguamide; oxalyldibiguamide; malonyldibiguamide; succinyldibiguamide; glutaryldibiguamide; adipyldibiguamide; pimelyldibiguamide; suberyldibiguamide; phthalyldibiguamide; paludrine; polyhexamethylene biguamide; 2-guanidinothiazole; 2-guanidinooxazole; 2-guanidinoimidazole; 3-guanidinopyrazole; 3-guanidino-1,2,4-triazole; 5-guanidinotetrazole; alexidine; buformin; and moroxydine.
[0166] N Valence Stabilizer #20: Examples of diamidinomethanes, bis(diamidinomethanes), and poly(diamidinomethanes) (N—N bidentates, N—N tridentates, N—N tetradentates, and N—N hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diamidinomethane; N-methyldiamidinomethane; N-ethyldiamidinomethane; N-isopropyldiamidinomethane; N-butyldiamidinomethane; N-benzyldiamidinomethane; N-phenyldiamidinomethane; N-tolyldiamidinomethane; N-naphthyldiamidinomethane; N-cyclohexyldiamidinomethane; N-norbornyldiamidinomethane; N-adamantyldiamidinomethane; dimethyldiamidinomethane; diethyldiamidinometbane; diisopropyldiamidinomethane; dibutyldiamidinomethane; dibenzyldiamidinomethane; diphenyldiamidinomethane; ditolyldiamidinomethane; dinaphthyldiamidinomethane; dicyclohexyldiamidinomethane; dinorbornyldiamidinomethane; diadamantyldiamidinomethane; ethylenebisdiamidinomethane; propylenebisdiamidinomethane; tetramethylenebisdiamidinomethane; pentamethylenebisdiamidinomethane; hexamethylenebisdiamidinomethane; heptamethylenebisdiamidinomethane; octamethylenebisdiamidinomethane; phenylenebisdiamidinomethane; piperazinebisdiamidinomethane; oxalylbisdiamidinomethane; malonylbisdiamidinomethane; succinylbisdiamidinomethane; glutarylbisdiamidinomethane; phthalylbisdiamidinomethane; 2-ainidinomethylthiazole; 2-amidinomethyloxazole; 2-amidinomethylimidazole; 3-amidinomethylpyrazole; 3-amidinomethyl-1,2,4-triazole; and 5-amidinomethyltetrazole.
[0167] N Valence Stabilizer #21: Examples of imidoylguanidines, amidinoguanidines, bis(imidoylguanidines), bis(amidinoguanidines), poly(imidoylguanidines), and poly(amidinoguanidines) (N—N bidentates, N—N tridentates, N—N tetradentates, and N—N hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: acetimidoylguanidine; amidinoguanidine, benzimidoylguanidine; cyclohexylimidoylguanidine; pentafluorobenzimidoylguanidine; 2-N-imidoylaminothiazole; 2-N-imidoylaminooxazole; 2-N-imidoylaminoimidazole; 3-N-imidoylaminopyrazole; 3-N-imidoylamino-1,2,4-triazole; and 5-N-imidoylaminotetrazole.
[0168] N Valence Stabilizer #22: Examples of diformamidine oxides (dicarbonimidic diamides), tricarbonimidic diamides, tetracarbonimidic diamides, bis(diformamidine oxides), and poly(diformamidine oxides) (N—N bidentates, N—N tridentates, or N—N tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diformamidine oxide; methyldiformamidine oxide; ethyldiformamidine oxide; isopropyldiformamidine oxide; butyldiformamidine oxide; benzyldiformamidine oxide; phenyldiformamidine oxide; tolyldiformamidine oxide; naphthyldiformamidine oxide; cyclohexyldiformamidine oxide; norbornyldiformamidine oxide; adamantyldiformamidine oxide; dimethyldiformamidine oxide; diethyldiformamidine oxide; diisopropyldiformamidine oxide; dibutyldiformamidine oxide; dibenzyldiformamidine oxide; diphenyldiformamidine oxide; ditolyldiformamidine oxide; dinaphthyldiformamidine oxide; dicyclohexyldiformamidine oxide; dinorbornyldiformamidine oxide; diadamantyldiformamidine oxide; 2-O-amidinohydroxythiazole; 2-O-amidinohydroxyoxazole; 2-O-amidinohydroxyimidazole; 3-O-amidinohydroxypyrazole; 3-O-amidinohydroxy-1,2,4-triazole; and 5-O-amidinohydroxytetrazole.
[0169] N Valence Stabilizer #23: Examples of diformamidine sulfides (thiodicarbonimidic diamides), thiotricarbonimidic diamides, thiotetracarbonimidic diamides, bis(diformamidine sulfides), and poly(diformamidine sulfides) (N—N bidentates, N—N tridentates, or N—N tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diformamidine sulfide; methyldiformamidine sulfide; ethyldiformamidine sulfide; isopropyldiformamidine sulfide; butyldiformamidine sulfide; benzyldiformamidine sulfide; phenyldiformamidine sulfide; tolyldiformamidine sulfide; naphthyldiformamidine sulfide; cyclohexyldiformamidine sulfide; norbornyldiformamidine sulfide; adamantyldiformamidine sulfide; dimethyldiformamidine sulfide; diethyldiformamidine sulfide; diisopropyldiformamidine sulfide; dibutyldiformamidine sulfide; dibenzyldiformamidine sulfide; diphenyldiformamidine sulfide; ditolyldiformamidine sulfide; dinaphthyldiformamidine sulfide; dicyclohexyldiformamidine sulfide; dinorbornyldiformamidine sulfide; diadamantyldiformamidine sulfide; phenylthiobisformamidine; 2-S-amidinomercaptothiazole; 2-S-amidinomercaptooxazole; 2-S-amidinomercaptoimidazole; 3-S-amidinomercaptopyrazole; 3-S-amidinomercapto-1,2,4-triazole; and 5-S-amidinomercaptotetrazole.
[0170] N Valence Stabilizer #24: Examples of imidodicarbonimidic acids, diimidodicarbonimidic acids, imidotricarbonimidic acids, imidotetracarbonimidic acids, and derivatives thereof (N—N Bidentates, N—N Tridentates, N—N Tetradentates, and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: imidodicarbonimidic acid, diimidodicarbonimidic acid, imidotricarbonimidic acid, imidotetracarbonimidic acid; O-methylimidodicarbonimidic acid; O-ethylimidodicarbonimidic acid; O-isopropylimidodicarbonimidic acid; O-phenylimidodicarbonimidic acid; O-benzylimidodicarbonimidic acid; O-cyclohexylimidodicarbonimidic acid; O-naphthylimidodicarbonimidic acid; O-norbornylimidodicarbonimidic acid; O-adamantylimidodicarbonimidic acid; O,O′-dimethylimidodicarbonimidic acid; O,O′-diethylimidodicarbonimidic acid; O,O′-diisopropylimidodicarbonimidic acid; O,O′-diphenylimidodicarbonimidic acid; O,O′-dibenzylimidodicarbonimidic acid; O,O′-dicyclohexylimidodicarbonimidic acid; O,O′-dinaphthylimidodicarbonimidic acid; O,O′-dinorbornylimidodicarbonimidic acid; and O,O′-diadamantylimidodicarbonimidic acid.
[0171] N Valence Stabilizer #25: Examples of thioimidodicarbonimidic acids, thiodiimidodicarbonimidic acids, thioimidotricarbonimidic acids, thioimidotetracarbonimidic acids, and derivatives thereof (N—N Bidentates, N—N Tridentates, N—N Tetradentates, and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: thioimidodicarbonimidic acid, thiodiimidodicarbonimidic acid, thioimidotricarbonimidic acid, thioimidotetracarbonimidic acid; O-methylthioimidodicarbonimidic acid; O-ethylthioimidodicarbonimidic acid; O-isopropylthioimidodicarbonimidic acid; O-phenylthioimidodicarbonimidic acid; O-benzylthioimidodicarbonimidic acid; O-cyclohexylthioimidodicarbonimidic acid; O-naphthylthioimidodicarbonimidic acid; O-norbornylthioimidodicarbonimidic acid; O-adamantylthioimidodicarbonimidic acid; O,O′-dimethylthioimidodicarbonimidic acid; O,O′-diethylthioimidodicarbonimidic acid; O,O′-diisopropylthioimidodicarbonimidic acid; O,O′-diphenylthioimidodicarbonimidic acid; O,O′-dibenzylthioimidodicarbonimidic acid; O,O′-dicyclohexylthioimidodicarbonimidic acid; O,O′-dinaphthylthioimidodicarbonimidic acid; O,O′-dinorbornylthioimidodicarbonimidic acid; and O,O′-diadamantylthioimidodicarbonimidic acid.
[0172] N Valence Stabilizer #26: Examples of diimidoylimines, diimidoylhydrazides, bis(diimidoylimines), bis(diimidoylhydrazides), poly(diimidoylimines), and poly(diimidoylhydrazides) (N—N Tridentates and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diacetimidoylimine; dibenzimidoylimine; and dicyclohexylimidoylimine.
[0173] N Valence Stabilizer #27: Examples of imidosulfamides, diimidosulfamides, bis(imidosulfamides), bis(diimidosulfamides), poly(imidosulfamides), and poly(diimidosulfamides) (N—N Bidentates, N—N Tridentates, N—N Tetradentates, and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: imidosulfamidic acid, diimidosulfamidic acid; O-phenylimidosulfamide; O-benzylimidosulfamide; N-phenylimidosulfamide; N-benzylimidosulfamide; O-phenyldiimidosulfamide; O-benzyldiimidosulfamide; N-phenyldiimidosulfamide; and N-benzyldiimidosulfamide.
[0174] N Valence Stabilizer #28: Examples of phosphoramidimidic triamides, bis(phosphoramidimidic triamides), and poly(phosphoramidimidic triamides) and derivatives thereof (N—N Bidentates, N—N Tridentates, N—N Tetradentates, and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: phosphoramidimidic triamide; N-phenylphosphoramidimidic triamide; N-benzylphosphoramidimidic triamide; N-naphthylphosphoramidimidic triamide; N-cyclohexylphosphoramidimidic triamide; N-norbornylphosphoramidimidic triamide; N,N′-diphenylphosphorainidimidic triamide; N,N′-dibenzylphosphoramidimidic triamide; N,N′-dinaphthylphosphoramidimidic triamide; N,N′-dicyclohexylphosphoramidimidic triamide; and N,N′-dinorbornylphosphoramidimidic triamide.
[0175] N Valence Stabilizer #29: Examples of phosphoramidimidic acid, phosphorodiamidimidic acid, bis(phosphoramidimidic acid), bis(phosphorodiamidimidic acid), poly(phosphoramidimidic acid), poly(phosphorodiamidimidic acid), and derivatives thereof (N—N Bidentates, N—N Tridentates, N—N Tetradentates, and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: phosphoramidimidic acid, phosphorodiamidimidic acid, O-phenylphosphoramidimidic acid; O-benzylphosphoramidimidic acid; O-naphthylphosphoramidimidic acid; O-cyclohexylphosphoramidimidic acid; O-norbornylphosphorainidimidic acid; O,O′-diphenylphosphoramidimidic acid; O,O′-dibenzylphosphoramidimidic acid; O,O′-dinaphthylphosphoramidimidic acid; O,O′-dicyclohexylphosphoramidimidic acid; and O,O′-dinorbornylphosphoramidimidic acid.
[0176] N Valence Stabilizer #30: Examples of phosphoramidimidodithioic acid, phosphorodiamidimidothioic acid, bis(phosphoramidimidodithioic acid), bis(phosphorodiamidimidothioic acid), poly(phospboramidimidodithioic acid), poly(phosphorodiamidimidothioic acid), and derivatives thereof (N—N Bidentates, N—N Tridentates, N—N Tetradentates, and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: phosphoramidimidodithioic acid, phosphorodiamidimidothioic acid, S-phenylphosphoramidimidodithioic acid; S-benzylphosphoramidimidodithoic acid; S-naphthylphosphoramidimidodithioic acid; S-cyclohexylphosphoramidimidodithioic acid; S-norbornylphosphoramidimidodithioic acid; S,S′-diphenylphosphoramidimidodithioic acid; S,S′-dibenzylphosphoramidimidodithioic acid; S,S′-dinaphthylphosphoramidimidodithioic acid; S,S′-dicyclohexylphosphoramidimidodithioic acid; and S,S′-dinorbornylphosphoramidimidodithioic acid.
[0177] N Valence Stabilizer #31: Examples of azo compounds with amino, imino, oximo, diazeno, or hydrazido substitution at the ortho- (for aryl) or alpha- or beta- (for alkyl) positions, bis[o-(H2N—) or alpha- or beta-(H2N—)azo compounds], or poly[o-(H2N—) or alpha- or beta-(H2N—)azo compounds) (N—N Bidentates, N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: o-aminoazobenzene; o,o′-diaminoazobenzene; (2-pyridine)azobenzene; 1-phenylazo-2-naphthylamine; pyridineazo-2-naphthol (PAN); pyridineazoresorcinol (PAR); o-hydroxy-o′-(beta-aminoethylamino)azobenzene; Benzopurpurin 4B; Congo Red; Fat Brown RR; benzopurpurin; Congo Red; Direct Red 75; Mordant Brown 48; Nitro Red; 2-imidazolylazobenzene; 2-benzimidazolylazobenzene; 3-pyrazolylazobenzene; 3-(1,2,4-triazolyl)azobenzene; 2-pyridylazobenzene; 2-pyrazinylazobenzene; and 2-pyrimidinylazobenzene.
[0178] N Valence Stabilizer #32: Examples of diazeneformimidamides (diazeneamidines), diazeneacetimidamides (diazene-alpha-amidinoalkanes(alkenes)), bis(diazeneformimidamides), bis(diazeneacetimidamides), poly(diazeneformimidamides), and poly(diazeneacetimidamides) (N—N Bidentates, N—N Tetradentates, and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diazeneformimidamide (diazeneamidine); diazeneacetimidamide (diazene-alpha-amidinomethane); phenyldiazeneformimidamide; triphenyldiazeneformimidamide; phenyldiazeneacetimidamide; and triphenyldiazeneacetimidamide.
[0179] N Valence Stabilizer #33: Examples of diazeneformimidic acid, diazeneacetimidic acid, bis(diazeneformimidic acid), bis(diazeneacetimidic acid), poly(diazeneformimidic acid), poly(diazeneacetimidic acid), and derivatives thereof (N—N Bidentates, N—N Tetradentates, and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diazeneformimidic acid, diazeneacetimidic acid, phenyldiazeneformimidic acid, diphenyldiazeneformimidic acid, phenyldiazeneacetimidic acid, and diphenyldiazeneacetimidic acid.
[0180] N Valence Stabilizer #34: Examples of diazeneformimidothioic acid, diazeneacetimidothioic acid, bis(diazeneformimidothioic acid), bis(diazeneacetimidothioic acid), poly(diazeneformimidothioic acid), poly(diazeneacetimidothioic acid), and derivatives thereof (N—N Bidentates, N—N Tetradentates, and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diazeneformimidothioic acid, diazeneacetimidothioic acid, phenyldiazeneformimidothioic acid, diphenyldiazeneformimidothioic acid, phenyldiazeneacetimidothioic acid, and diphenyldiazeneacetimidothioic acid.
[0181] N Valence Stabilizer #35: Examples of imidoyldiazenes, bis(imidoyldiazenes), and poly(imidoyldiazenes), (N—N Tridentates and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: acetimidoyldiazene; benzimidoyldiazene; and cyclohexylimidoyldiazene.
[0182] N Valence Stabilizer #36: Examples of diazenediformimidamides (1,2-diazenediamidines), diazenediacetimidamides (1,2-diazene-di-alpha-amidinoalkanes(alkenes)), bis(diazenediformimidamides), bis(diazenediacetimidamides), poly(diazenediformimidamides), and poly(diazenediacetimidamides) (N—N Tridentates and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diazenediformimidamide (1,2-diazenediamidine), diazenediacetimidamide (1,2-diazene-di-alpha-amidinomethane); diphenyldiazenediformimidamide; tetraphenyldiazenediformimidamide; diphenyldiazenediacetimidamide; and tetraphenyldiazenediacetimidamide.
[0183] N Valence Stabilizer #37: Examples of diazenediformimidic acid, diazenediacetimidic acid, bis(diazenediformimidic acid), bis(diazenediacetimidic acid), poly(diazenediformimidic acid), and poly(diazenediacetimidic acid), and derivatives thereof (N—N Tridentates and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diazenediformimidic acid, diazenediacetimidic acid, diphenyldiazenediformimidic acid, and diphenyldiazenediacetimidic acid.
[0184] N Valence Stabilizer #38: Examples of diazenediformimidothioic acid, diazenediacetimidothioic acid, bis(diazenediformimidothioic acid), bis(diazenediacetimidothioic acid), poly(diazenediformimidothioic acid), and poly(diazenediacetimidothioic acid), and derivatives thereof (N—N Tridentates and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diazenediformimidothioic acid, diazenediacetimidothioic acid, diphenyldiazenediformimidothioic acid, and diphenyldiazenediacetimidothioic acid.
[0185] N Valence Stabilizer #39: Examples of diimidoyldiazenes, bis(diimidoyldiazenes), and poly(diimidoyldiazenes), (N—N Tridentates and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diacetimidoyldiazene; dibenzimidoyldiazene; and dicyclohexylimidoyldiazene.
[0186] N Valence Stabilizer #40: Examples of ortho-amino (or -hydrazido) substituted formazans, bis(o-amino or -hydrazido substituted formazans), and poly(o-amino or -hydrazido substituted formazans) (N—N Bidentates, N—N Tridentates, N—N Tetradentates, and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 1-(2-aminophenyl)-3,5-diphenylformazan; and 1,5-bis(2-aminophenyl)-3-phenylformazan.
[0187] N Valence Stabilizer #41: Examples of ortho-amino (or -hydrazido) substituted azines (including ketazines), bis(o-amino or hydrazido substituted azines), and poly(o-amino or hydrazido substituted azines) (N—N Bidentates, N—N Tridentates, N—N Tetradentates, and N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-amino-1-benzalazine; 2-amino-1-naphthalazine; and 2-amino-1-cyclohexanonazine.
[0188] N Valence Stabilizer #42: Examples of Schiff Bases with one Imine (C═N) Group and with ortho- or alpha- or beta-amino or imino or oximo or diazeno or hydrazido substitution (N—N Bidentates, N—N Tridentates, N—N Tetradentates, N—N Pentadentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N-(2-Aminobenzaldehydo)isopropylamine; N-(2-Pyridinecarboxaldehydo)isopropylamine; N-(2-Pyrrolecarboxaldehydo)isopropylamine; N-(2-Acetylpyridino)isopropylamine; N-(2-Acetylpyrrolo)isopropylamine; N-(2-Aminoacetophenono)isopropylamine; N-(2-Aminobenzaldehydo)cyclohexylamine; N-(2-Pyridinecarboxaldehydo)cyclohexylamine; N-(2-Pyrrolecarboxaldehydo)cyclohexylamine; N-(2-Acetylpyridino)cyclohexylamine; N-(2-Acetylpyrrolo)cyclohexylamine; N-(2-Aminoacetophenono)cyclohexylamine; N-(2-Aminobenzaldehydo)aniline; N-(2-Pyridinecarboxaldehydo)aniline; N-(2-Pyrrolecarboxaldehydo)aniline; N-(2-Acetylpyridino)aniline; N-(2-Acetylpyrrolo)aniline; N-(2-Aminoacetophenono)aniline; N-(2-Aminobenzaldehydo)aminonorbornane; N-(2-Pyridinecarboxaldehydo)aminonorbornane; N-(2-Pyrrolecarboxaldehydo)aminonorbornane; N-(2-Acetylpyridino)aminonorbornane; N-(2-Acetylpyrrolo)aminonorbornane; N-(2-Aminoacetophenono)aminonorbornane; 2-pyrrolecarboxaldehyde phenylhydrazone; 2-pyrrolecarboxaldehyde 2-pyridyl hydrazone; 2-aminobenzaldehyde phenylhydrazone (nitrin); and 2-aminobenzaldehyde 2-pyridyl hydrazone. Also includes hydrazones with ortho-N substitution.
[0189] N Valence Stabilizer #43: Examples of Schiff Bases with two Imine (C═N) Groups and without ortho- (for aryl constituents) or alpha- or beta- (for alkyl constituents) hydroxy, carboxy, carbonyl, thiol, mercapto, thiocarbonyl, amino, imino, oximo, diazeno, or hydrazido substitution (N—N Bidentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N,N′-(Glyoxalo)diisopropylamine; N,N′-(Glyoxalo)dicyclohexylamine; N,N′-(Glyoxalo)dianiline; N,N′-(Glyoxalo)di-aminonorbornane; N,N′-(Malondialdehydo)diisopropylamine; N,N′-(Malondialdehydo)dicyclohexylamine; N,N′-(Malondialdehydo)dianiline; N,N′-(Malondialdehydo)di-aminonorbornane; N,N′-(Phthalicdialdehydo)diisopropylamine; N,N′-(Phthalicdialdehydo)dicyclohexylamine; N,N′-(Phthalicdialdehydo)dianiline; N,N′-(Phthalicdialdehydo)di-aminonorbornane; N,N′-(Formylcamphoro)diisopropylamine; N,N′-(Formylcamphoro)dicyclohexylamine; N,N′-(Formylcamphoro)dianiline; N,N′-(Formylcamphoro)di-aminonorbornane; N,N′-(Acetylacetonato)diisopropylamine; N,N′-(Acetylacetonato)dicyclohexylamine; N,N′-(Acetylacetonato)dianiline; N,N′-(Acetyl acetonato)di-aminonorbornane; N,N′-(Diacetylbenzeno)diisopropylamine; N,N′-(Diacetylbenzeno)dicyclohexylamine; N,N′-(Diacetylbenzeno)dianiline; N,N′-(Diacetylbenzeno)di-aminonorbornane; N,N′-(1,2-Cyclohexanono)diisopropylamine; N,N′-(1,2-Cyclohexanono)dicyclohexylamine; N,N′-(1,2-Cyclohexanono)dianiline; N,N′-(1,2-Cyclohexanono)di-aminonorbornane; N,N′-(Camphorquinono)diisopropylamine; N,N′-(Camphorquinono)dicyclohexylamine; N,N′-(Camphorquinono)dianiline; N,N′-(Camphorquinono)di-aminonorbornane; N,N′-(Benzaldehydo)ethylenediamine; N,N′-(Naphthaldehydo)ethylenediamine; N,N′-(Acetophenono)ethylenediamine; N,N′-(Benzaldehydo)trimethylenediamine; N,N′-(Naphthaldehydo)trimethylenediamine; N,N′-(Acetophenono)trimethylenediamine; N,N′-(Benzaldehydo)cyclohexane-1,2-diamine; N,N′-(Naphthaldehydo)cyclohexane-1,2-diamine; N,N′-(Acetophenono)cyclohexane-1,2-diamine; N,N′-(Benzaldehydo)-1,2-diaminobenzene; N,N′-(Naphthaldehydo)-1,2-diaminobenzene; N,N′-(Acetophenono)-1,2-diaminobenzene; N,N′-(Acetylacetonato)ethylenediamine; N,N′-(Acetylacetonato)-1,2-cyclohexylenediamine; N,N′-(Acetylacetonato)-1,2-propylenediamine; N,N′-(Glyoxalo)-o-phenylenediamine; and N,N′-(Glyoxalo)ethylenediamine. Also includes dihydrazones.
[0190] N Valence Stabilizer #44: Examples of Schiff Bases with two Imine (C═N) Groups and with ortho- or alpha- or beta-amino or imino or oximo or diazeno or hydrazido substitution (N—N Bidentates, N—N Tridentates, N—N Tetradentates, N—N Pentadentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N,N′-(2,6-Pyridinedicarboxaldehydo)diisopropylamine; N,N′-(2,6-Pyridinedicarboxaldehydo)dicyclohexylamine; N,N′-(2,6-Pyridinedicarboxaldehydo)dianiline; N,N′-(2,6-Pyridinedicarboxaldehydo)di-aminonorbornane; N,N′-(2,5-Pyrroledicarboxaldehydo)diisopropylamine; N,N′-(2,5-Pyrroledicarboxaldehydo)dicyclohexylamine; N,N′-(2,5-Pyrroledicarboxaldehydo)dianiline; N,N′-(2,5-Pyrroledicarboxaldehydo)di-aminonorbornane; N,N′-(o-Aminophthalicdialdehydo)diisopropylamine; N,N′-(o-Aminophthalicdialdehydo)dicyclohexylamine; N,N′-(o-Aminophthalicdialdehydo)dianiline; N,N′-(o-Aminophthalicdialdehydo)di-aminonorbornane; N,N′-(o-Aminoformylcamphoro)diisopropylamine; N,N′-(o-Aminoformylcamphoro)dicyclohexylamine; N,N′-(o-Aminoformylcamphoro)dianiline; N,N′-(o-Aminoformylcamphoro)di-aminonorbornane; N,N′-(2,6-Diacetylpyridino)diisopropylamine; N,N′-(2,6-Diacetylpyridino)dicyclohexylamine; N,N′-(2,6-Diacetylpyridino)dianiline; N,N′-(2,6-Diacetylpyridino)di-aminonorbornane; N,N′-(o-Aminodiacetylbenzeno)diisopropylamine; N,N′-(o-Aminodiacetylbenzeno)dicyclohexylamine; N,N′-(o-Aminodiacetylbenzeno)dianiline; N,N′-(o-Aminodiacetylbenzeno)di-aminonorbornane; N,N′-(3,6-Diamino-1,2-cyclohexanono)diisopropylamine; N,N′-(3,6-Diamino-1,2-cyclohexanono)dicyclohexylamine; N,N′-(3,6-Diamino-1,2-cyclohexanono)dianiline; N,N′-(3,6-Diamino-1,2-cyclohexanono)di-aminonorbornane; N,N′-(2,5-Diacetylpyrrolo)diisopropylamine; N,N′-(2,5-Diacetylpyrrolo)dicyclohexylamine; N,N′-(2,5-Diacetylpyrrolo)dianiline; N,N′-(2,5-Diacetylpyrrolo)di-aminonorbornane; N,N′-(o-Aminobenzaldehydo)ethylenediamine; N,N′-(o-Aminonaphthaldehydo)ethylenediamine; N,N′-(o-Aminoacetophenono)ethylenediamine; N,N′-(o-Aminobenzaldehydo)trimethylenediamine; N,N′-(o-Aminonaphthaldehydo)trimethylenediamine; N,N′-(o-Aminoacetophenono)trimethylenediamine; N,N′-(o-Aminobenzaldehydo)cyclohexane-1,2-diamine; N,N′-(o-Aminonaphthaldehydo)cyclohexane-1,2-diamine; N,N′-(o-Aminoacetophenono)cyclohexane-1,2-diamine; N,N′-(o-Aminobenzaldehydo)-1,2-diaminobenzene; N,N′-(o-Aminonaphthaldehydo)-1,2-diaminobenzene; and N,N′-(o-Aminoacetophenono)-1,2-diaminobenzene. Also includes hydrazones with ortho-N substitution.
[0191] N Valence Stabilizer #45: Examples of Schiff Bases with three Imine (C—N) Groups and without ortho- (for aryl constituents) or alpha- or beta- (for alkyl constituents) hydroxy, carboxy, carbonyl, thiol, mercapto, thiocarbonyl, amino, imino, oximo, diazeno, or hydrazido substitution (N—N Tridentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N,N′,N″-(Benzaldehydo)tris(2-aminoethyl)amine; N,N′,N″-(Naphthaldehydo)tris(2-aminoethyl)amine; and N,N′,N″-(Acetophenono)tris(2-aminoethyl)amine. Also includes trihydrazones.
[0192] N Valence Stabilizer #46: Examples of Schiff Bases with three Imine (C═N) Groups and with ortho- or alpha- or beta-amino or imino or oximo or diazeno or hydrazido substitution (N—N Tridentates, N—N Tetradentates, N—N Pentadentates, or N—N Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N,N′,N″-(o-Aminobenzaldehydo)tris(2-aminoethyl)amine; N,N′,N″-(o-Aminonaphthaldehydo)tris(2-aminoethyl)amine; and N,N′,N″-(o-Aminoacetophenono)tris(2-aminoethyl)amine.
[0193] S Valence Stabilizer #1: Examples of macrocyclic, macrobicyclic, and macropolycyclic oligothioketones (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of thioketones (especially in the beta position) (S—S Bidentates, S—S Tetradentates, and S—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: hexathioketocyclotetracosane ([24]ane(═S)6); hexathioketocycloheneicosane ([21]ane(═S)6); hexathioketocyclooctadecane ([18]ane(═S)6); hexathioketocyclopentadecane ([15]ane(S)6); tetrathioketocycloeicosane ([20]ane(═S)4); tetrathioketocyclooctadecane ([18]ane(═S)4); tetrathioketocyclohexadecane ([16]ane(═S)4); tetrathioketocyclotetradecane ([14]ane(S)4); tetrathioketocyclododecane ([12]ane(═S)4); dithioketocyclohexadecane ([16]ane(═S)2); dithioketocyclotetraadecane ([14]ane(═S)2); dithioketocyclododecane ([12]ane(═S)2); dithioketocyclodecane ([1]ane(S)2); and dithioketocyclooctane ([8]ane(═S)2).
[0194] S Valence Stabilizer #2: Examples of macrocyclic, macrobicyclic, and macropolycyclic dithiolenes (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of alpha-, alpha-dithiolenes (meaning two thiol groups on a single carbon atom in the ring) (S—S Bidentates, S—S Tetradentates, and S—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: hexathiolocyclotetracosane ([24]ane(—SH)6); hexathiolocycloheneicosane ([21]ane(—SH)6); hexathiolocyclooctadecane ([18]ane(—SH)6); hexathiolocyclopentadecane ([15]ane(—SH)6); tetrathiolocycloeicosane ([20]ane(—SH)4); tetrathiolocyclooctadecane ([18]ane(—SH)4); tetrathiolocyclohexadecane ([16]ane(—SH)4); tetrathiolocyclotetradecane ([14]ane(—SH)4); tetrathiolocyclododecane ([12]ane(—SH)4); dithiolocyclohexadecane ([16]ane(—SH)2); dithiolocyclotetraadecane ([14]ane(—SH)2); dithiolocyclododecane ([12]ane(—SH)2); dithiolocyclodecane ([11]ane(—SH)2); and dithiolocyclooctane ([8]ane(—SH)2).
[0195] S Valence Stabilizer #3: Examples of dithioimidodialdehydes, dithiohydrazidodialdehydes (thioacyl thiohydrazides), bis(dithioimidodialdehydes), bis(dithiohydrazidodialdehydes), poly(ditbioimidodialdehydes), and poly(dithiohydrazidodialdehydes) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiodiacetamide, dithiodipropanamide, dithiodibutanamide, dithiodibenzamide, and dithiodicyclohexamide.
[0196] S Valence Stabilizer #4: Examples of dithioimidodicarbonic acids, dithiohydrazidodicarbonic acids, bis(dithioimidodicarbonic acids), bis(dithiohydrazidodicarbonic acids), poly(dithioimidodicarbonic acids), poly(dithiohydrazidodicarbonic acids) and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithioimidodicarbonic acid, dithiohydrazidodicarbonic acid, O-pbenyldithioimidodicarbonic acid, O-benzyldithioimidodicarbonic acid, O-cyclohexyldithioimidodicarbonic acid, O-norbornyldithioimidodicarbonic acid, O,O′-diphenyldithioimidodicarbonic acid, O,O′-dibenzyldithioimidodicarbonic acid, O,O′-dicyclohexyldithioimidodicarbonic acid, and O,O′-norbornyldithioimidodicarbonic acid.
[0197] S Valence Stabilizer #5: Examples of 1,3-dithioketones (dithio-beta-ketonates), 1,3,5-trithioketones, bis(1,3-dithioketones), and poly(1,3-dithioketones) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: hexafluoropentanedithione; 1,3-diphenyl-1,3-propanedithione; thiobenzoylthiopinacolone; dithiocyclohexoylmethane; diphenylpentanetrithionate; tetramethylnonanetrithionate; bexafluoroheptanetrithionate; trifluoroheptanetrithionate; 1-(2-thienyl)-1,3-butanedithione, 1-(2-naphthyl)-1,3-butanedithione, trifluorothioacetylthiocampbor; and 1,3-indandithione.
[0198] S Valence Stabilizer #6: Examples of 1,2-dithioketones (dithiolenes, dithio-alpha-ketonates), 1,2,3-trithioketones, dithiotropolonates, o-dithioquinones, bis(1,2-dithioketones), and poly(1,2-dithioketones) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiotropolone; 1,2-dithiobenzoquinone (o-dithioquinone)(o-benzenedithiolate)(bdt); di-tert-butyl-1,2-dithiobenzoquinone; hexafluoro-1,2-dithiobenzoquinone; 1,2-ditbionaphthoquinone; 9,10-dithiophenanthroquinone; ethylenedithiolene (edt); maleonitriledithiolene (mnt); trifluoromethyldithiolene (tfd); carbomethoxydithiolene (cmt); trithionedithiolene (dmit); toluenedithiolate (tdt); dithiomanaldehyde (propenethionethiolate)(ptt); dithioacetylacetonate (SacSac); dijulolidinedithiolene; 2,3-piperazinedithiolate; di(4-aminophenyl)dithiolene; dimercaptoisotrithione (dmit); (4-octylphenyl)dithiolene; benzenetetrathiol; tetrathiosquaric acid; trithiodeltic acid; pentathiocroconic acid; dithiocroconic acid; hexathiorhodizonic acid; dithiorhodizonic acid; ethylenetetrathiol; trans-butadienetetrathiolate; tetrathiooxalic acid; 1,2-indandithione; naphthothioquinone; acenapthenethioquinone; aceanthrenethioquinone; and indole-2,3-dithione (thioisatin).
[0199] S Valence Stabilizer #7: Examples of dithiomalonamides (dithiomalonodiamides), bis(dithiomalonamides), and polydithiomalonamides (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiomalonamide, N-phenyldithiomalonamide, N-benzyldithiomalonamide, N-pentafluorophenyldithiomalonamide, N-cyclohexyldithiomalonamide, N-norbornyldithiomalonamide, N,N′-diphenyldithiomalonamide, N,N′-dibenzyldithiomalonamide, N,N′-dipentafluorophenyldithiomalonamide, N,N′-dicyclohexyldithiomalonamide, and N,N′-norbornyldithiomalonamide.
[0200] S Valence Stabilizer #8: Examples of 2-thioacylthioacetamides, bis(2-thioacylthioacetamides), and poly(2-thioacylthioacetamides) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-thioacetothioacetamide, N-phenyl-2-thioacetothioacetamide, N-pentafluorophenyl-2-thioacetothioacetamide, N-benzyl-2-thioacetothioacetamide, N-cyclohexyl-2-thioacetothioacetamide, N-norbornyl-2-thioacetothioacetamide, N-phenyl-2-thiobenzothioacetamide, N-pentafluorophenyl-2-pentafluorothiobenzothioacetamide, and N-cyclohexyl-2-thiocyclohexothioacetamide.
[0201] S Valence Stabilizer #9: Examples of dithioacyl sulfides, bis(dithioacyl sulfides), and poly(dithioacyl sulfides), (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithioacetyl sulfide; dithiopropanoyl sulfide; dithiobenzoyl sulfide; and dithiopentafluorobenzoyl sulfide.
[0202] S Valence Stabilizer #10: Examples of trithiodicarbonic diamides, bis(trithiodicarbonic diamides), and poly(trithiodicarbonic diamides) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: trithiodicarbonic diamide; N-phenyltrithiodicarbonic diamide; N-pentafluorophenyltrithiodicarbonic diamide; N-benzyltrithiodicarbonic diamide; N-cyclohexyltrithiodicarbonic diamide; N-norbornyltrithiodicarbonic diamide; N,N′-diphenyltrithiodicarbonic diamide; N,N′-dipentafluorophenyltrithiodicarbonic diamide; N,N′-dibenzyltrithiodicarbonic diamide; N,N′-dicyclohexyltrithiodicarbonic diamide; and N,N′-dinorbornyltrithiodicarbonic diamide.
[0203] S Valence Stabilizer #11: Examples of pentathio-, tetrathio-, or trithiodicarbonic acids, bis(pentathio-, tetrathio-, or trithiodicarbonic acids), poly(pentathio-, tetrathio-, or trithiodicarbonic acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: pentathiodicarbonic acid, tetrathiodicarbonic acid, trithiodicarbonic acid, O-phenyltrithiodicarbonic acid, O-benzyltrithiodicarbonic acid, O-cyclohexyltrithiodicarbonic acid, O-norbornyltrithiodicarbonic acid, O,O′-diphenyltrithiodicarbonic acid, O,O′-dibenzyltrithiodicarbonic acid, O,O′-dicyclohexyltrithiodicarbonic acid, and O,O′-dinorbornyltrithiodicarbonic acid.
[0204] S Valence Stabilizer #12: Examples of dithiohypophosphoric acids, bis(dithiohypophosphoric acids), poly(dithiohypophosphoric acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiohypophosphoric acid, methyldithiohypophosphoric acid, isopropyldithiohypophosphoric acid, tert-butyldithiohypophosphoric acid, phenyldithiohypophosphoric acid, pentafluorophenyldithiohypophosphoric acid, benzyldithiohypophosphoric acid, cyclohexyldithiohypophosphoric acid, norbornyldithiohypophosphoric acid, dimethyldithiohypophosphoric acid, diisopropyldiothiohypophosphoric acid, di-tert-butyldithiohypophosphoric acid, diphenyldithiohypophosphoric acid, dipentafluorophenyldithiohypophosphoric acid, dibenzyldithiohypophosphoric acid, dicyclohexyldithiohypophosphoric acid, and dinorbornyldithiohypophosphoric acid.
[0205] S Valence Stabilizer #13: Examples of dithiohypophosphoramides, bis(dithiohypophosphoramides), and poly(dithiohypophosphoramides) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiohypophosphoramide, N-methyldithiohypophosphoramide, N-isopropyldithiohypophosphoramide, N-tert-butyldithiohypophosphoramide, N-phenyldithiohypophosphoramide, N-pentafluorophenyldithiohypophosphoramide, N-benzyldithiohypophosphoramide, N-cyclohexyldithiohypophosphoramide, N-norbornyldithiohypophosphoramide, N,N′″-dimethyldithiohypophosphoramide, N,N′″-diisopropyldithiohypophosphoramide, N,N′″-di-tert-butyldithiohypophosphoramide, N,N′″-diphenyldithiohypophosphoramide, N,N′″-di-pentafluorophenyldithiohypophosphoramide, N,N′″-dibenzyldithiohypophosphoramide, N,N′″-dicyclohexyldithiohypophosphoramide, and N,N′″-dinorbornyldithiohypophosphoramide.
[0206] S Valence Stabilizer #14: Examples of dithioimidodiphosphoric acids, dithiohydrazidodiphosphoric acids, bis(dithioimidodiphosphoric acids), bis(dithiohydrazidodiphosphoric acids), poly(dithioimidodiphosphoric acids), poly(dithiohydrazidodiphosphoric acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithioimidodiphosphoric acid, methyldithioimidodiphosphoric acid, isopropyldithioimidodiphosphoric acid, tert-butyldithioimidodiphosphoric acid, phenyldithioimidodiphosphoric acid, pentafluorophenyldithioimidodiphosphoric acid, benzyldithioimidodiphosphoric acid, cyclohexyldithioimidodiphosphoric acid, norbornyldithioimidodiphosphoric acid, dimethyldithioimidodiphosphoric acid, diisopropyldiothioimidodiphosphoric acid, di-tert-butyldithioimidodiphosphoric acid, diphenyldithioimidodiphosphoric acid, di-pentafluorophenyldithioimidodiphosphoric acid, dibenzyldithioimidodiphosphoric acid, dicyclohexyldithioimidodiphosphoric acid, and dinorbornyldithioimidodiphosphoric acid.
[0207] S Valence Stabilizer #15: Examples of dithioimidodiphosphoramides, dithiohydrazidodiphosphoramides, bis(dithioimidodiphosphoramides), bis(dithiohydrazidodiphosphoramides), poly(dithioimidodiphosphoramides), and poly(dithiohydrazidodiphosphoramides) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithioimidodiphosphoramide, N-methyldithioimidodiphosphoramide, N-isopropyldithioimidodiphosphoramide, N-tert-butyldithioimidodiphosphoramide, N-phenyldithioimidodiphosphoramide, N-pentafluorophenyldithioimidodiphosphoramide, N-benzyldithioimidodiphosphoramide, N-cyclohexyldithioimidodiphosphoramide, N-norbornyldithioimidodiphosphoramide, N,N′″-dimethyldithioimidodiphosphoramide, N,N′″-diisopropyldithioimidodiphosphoramide, N,N′″-di-tert-butyldithioimidodiphosphoramide, N,N′″-diphenyldithioimidodiphosphoramide, N,N′″-di-pentafluorophenyldithioimidodiphosphoramide, N,N′″-dibenzyldithioimidodiphosphoramide, N,N′″-dicyclohexyldithioimidodiphosphoramide, and N,N′″-dinorbornyldithioimidodiphosphoramide.
[0208] S Valence Stabilizer #16: Examples of dithiodiphosphoramides, bis(dithiodiphosphoramides), and poly(dithiodiphosphoramides) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiodiphosphoramide, N-methyldithiodiphosphoramide, N-isopropyldithiodiphosphoramide, N-tert-butyldithiodiphosphoramide, N-phenyldithiodiphosphoramide, N-pentafluorophenyldithiodiphosphoramide, N-benzyldithiodiphosphoramide, N-cyclohexyldithiodiphosphoramide, N-norbornyldithiodiphosphoramide, N,N′″-dimethyldithiodiphosphoramide, N,N′″-diisopropyldithiodiphosphoramide, N,N′″-di-tert-butyldithiodiphosphoramide, N,N′″-diphenyldithiodiphosphoramide, N,N′″-di-pentafluorophenyldithiodiphosphoramide, N,N′″-dibenzyldithiodiphospboramide, N,N′″-dicyclohexyldithiodiphosphoramide, and N,N′″-dinorbornyldithiodiphosphoramide.
[0209] S Valence Stabilizer #17: Examples of dithiodiphosphoric acids, bis(dithiodiphosphoric acids), poly(dithiodiphosphoric acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiodiphosphoric acid, methyldithiodiphosphoric acid, isopropyldithiodiphosphoric acid, tert-butyldithiodiphosphoric acid, phenyldithiodiphosphoric acid, pentafluorophenyldithiodiphosphoric acid, benzyldithiodiphosphoric acid, cyclohexyldithiodiphosphoric acid, norbornyldithiodiphosphoric acid, dimethyldithiodiphosphoric acid, diisopropyldiothiodiphosphoric acid, di-tert-butyldithiodiphosphoric acid, diphenyldithiodiphosphoric acid, di-pentafluorophenyldithiodiphosphoric acid, dibenzyldithiodiphosphoric acid, dicyclohexyldithiodiphosphoric acid, and dinorbornyldithiodiphosphoric acid.
[0210] S Valence Stabilizer #18: Examples of trithiophosphoric acids (phosphorotritbioic acids), bis(trithiophosphoric acids), poly(trithiophosphoric acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: trithiophosphoric acid, O-phenyltrithiophosphoric acid, O-benzyltrithiophosphoric acid, O-cyclohexyltrithiophosphoric acid, O-norbornyltrithiophosphoric acid, O,S-diphenyltrithiophosphoric acid, O,S-dibenzyltrithiophosphoric acid, O,S-dicyclohexyltrithiophosphoric acid, and O,S-dinorbornyltrithiophosphoric acid.
[0211] S Valence Stabilizer #19: Examples of dithiophosphoric acids (phosphorodithioic acids), bis(dithiophosphoric acids), poly(dithiophosphoric acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiophosphoric acid, O-phenyldithiophosphoric acid, O-benzyldithiophosphoric acid, O-cyclohexyldithiophosphoric acid, O-norbornyldithiophosphoric acid, O,O-diphenyldithiophosphoric acid, O,O-dibenzyldithiophosphoric acid, O,O-dicyclohexyldithiophosphoric acid, and O,O-dinorbornyldithiophosphoric acid.
[0212] S Valence Stabilizer #20: Examples of tetrathiophosphoric acids (phosphorotetrathioic acids), bis(tetrathiophosphoric acids), poly(tetrathiophosphoric acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: tetrathiophosphoric acid, S-phenyltetrathiophosphoric acid, S-benzyltetrathiophosphoric acid, S-cyclohexyltetrathiophosphoric acid, S-norbornyltetrathiophosphoric acid, S,S-diphenyltetrathiophosphoric acid, S,S-dibenzyltetrathiophosphoric acid, S,S-dicyclohexyltetrathiophosphoric acid, and S,S-dinorbornyltetrathiophosphoric acid.
[0213] S Valence Stabilizer #21: Examples of phosphoro(dithioperoxo)dithioic acids, bis[phosphoro(dithioperoxo)dithioic acids], poly[phosphoro(dithioperoxo)dithioic acids], and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+ include, but are not limited to: phosphoro(dithioperoxo)dithioic acid, O-phenylphosphoro(dithioperoxo)dithioic acid, O-benzylphosphoro(dithioperoxo)dithioic acid, O-cyclohexylphosphoro(dithioperoxo)dithioic acid, O-norbornylphosphoro(dithioperoxo)dithioic acid, O,S-diphenylphosphoro(dithioperoxo)dithioic acid, O,S-dibenzylphosphoro(dithioperoxo)ditbioic acid, O,S-dicyclohexylphosphoro(dithioperoxo)dithioic acid, and O,S-dinorbornylphosphoro(dithioperoxo)dithioic acid.
[0214] S Valence Stabilizer #22: Examples of phosphoro(dithioperoxo)thioic acids, bis[phosphoro(dithioperoxo)thioic acids], poly[phosphoro(dithioperoxo)thioic acids], and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: phosphoro(dithioperoxo)thioic acid, O-phenylphosphoro(dithioperoxo)thioic acid, O-benzylphosphoro(dithioperoxo)thioic acid, O-cyclohexylphosphoro(dithioperoxo)thioic acid, O-norbornylphosphoro(ditbioperoxo)thioic acid, O,S-diphenylphosphoro(dithioperoxo)thioic acid, O,S-dibenzylphosphoro(dithioperoxo)thioic acid, O,S-dicyclohexylphosphoro(dithioperoxo)thioic acid, and O,S-dinorbornylphosphoro(dithioperoxo)thioic acid.
[0215] S Valence Stabilizer #23: Examples of phosphoro(dithioperoxo)trithioic acids, bis[phosphoro(dithioperoxo)trithioic acids], poly[phosphoro(dithioperoxo)trithioic acids], and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: phosphoro(dithioperoxo)trithioic acid, O-phenylphosphoro(dithioperoxo)trithioic acid, O-benzylphosphoro(dithioperoxo)trithioic acid, O-cyclohexylphosphoro(dithioperoxo)trithioic acid, O-norbornylphosphoro(dithioperoxo)trithioic acid, O,S-diphenylphosphoro(dithioperoxo)trithioic acid, O,S-dibenzylphosphoro(dithioperoxo)trithioic acid, O,S-dicyclohexylphosphoro(dithioperoxo)trithioic acid, and O,S-dinorbornylphosphoro(dithioperoxo)trithioic acid.
[0216] S Valence Stabilizer #24: Examples of beta-mercaptothioketones, beta-mercaptothioaldehydes, bis(beta-mercaptothioketones), bis(beta-mercaptothioaldehydes), poly(beta-mercaptothioketones), and poly(beta-mercaptothioaldehydes) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 4-mercaptopentan-2-thione; 1,3-diphenyl-3-mercaptopropanethioaldehyde; 1,3-dibenzyl-3-mercaptopropanethioaldehyde; 1,3-dicyclohexyl-3-mercaptopropanethioaldehyde; 1,3-dinorbornyl-3-mercaptopropanethioaldehyde; 1,3-di(2-thienyl)-3-mercaptopropanethioaldehyde; 1,3-di(2-furyl)-3-mercaptopropanethioaldehyde; o-mercaptothioacetophenone; 5-mercapto-1,4-dithionaphthoquinone; 1-mercaptothioacridone; 1-mercaptodithioanthraquinone; 1,8-dimercaptodithioanthraquinone; and beta-mercaptothiobenzophenone.
[0217] S Valence Stabilizer #25: Examples of N-(aminomethylthiol)thioureas [N-(aminomercaptomethyl)thioureas], bis[N-(aminomethylthiol)thioureas], and poly[N-(aminomethylthiol)thioureas] (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N′-(aminomercaptomethyl)thiourea; N,N″-dimethyl-N′-(aminomercaptomethyl)thiourea; N,N′-diethyl-N′-(aminomercaptomethyl)thiourea; N,N″-isopropyl-N′-(aminomercaptomethyl)thiourea; N,N″-diphenyl-N′-(aminomercaptomethyl)thiourea; N,N″-dibenzyl-N′-(aminonercaptomethyl)thiourea; N,N″-dicyclohexyl-N′-(aminomercaptomethyl)thiourea; and N,N″-dinorbornyl-N′-(aminomercaptomethyl)thiourea.
[0218] S Valence Stabilizer #26: Examples of dithiooxamides, bis(dithiooxamides), and poly(dithiooxamides) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiooxamide (rubeanic acid), N-methyldithiooxamide; N-ethyldithiooxamide; N-isopropyldithiooxamide; N-phenyldithiooxamide; N-benzyldithiooxamide; N-cyclohexyldithiooxamide; N-norbornyldithiooxamide; N,N′-dimethyldithiooxamide; N,N′-diethyldithiooxamide; N,N′-diisopropyldithiooxamide; N,N′-diphenylditbiooxamide; N,N′-dibenzyldithiooxamide; N,N′-dicyclohexyldithiooxamide; and N,N′-dinorbornyldithiooxamide.
[0219] S Valence Stabilizer #27: Examples of 1,1-dithiolates, bis(1,1-dithiolates), and poly(1,1-dithiolates) (S—S Bidentates and S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 1,1-dicyano-2,2-ethylene dithiolate (i-mnt); 1,1-dicarboalkoxy-2,2-ethylene dithiolate (DED); 1,1-di(trifluoromethyl)-2,2-ethylenedithiolate; 1,1-di(pentafluorophenyl)-2,2-ethylenedithiolate; 1-pentamethylene-2,2-ethylene dithiolate; and 1-nitroethylene dithiolate.
[0220] S Valence Stabilizer #28: Examples of dithiomonocarboxylic acids, tri- and tetrathiodicarboxylic Acids, bis(dithiomonocarboxylic acids), bis(tri- and tetrathiodicarboxylic acids), poly(dithiomonocarboxylic acids), poly(tri- and tetrathiodicarboxylic acids), and derivatives thereof (S—S Bidentates and S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithioacetic acid; dithiopropionic acid; dithiobenzoic acid (dtb); dithiophenylacetic acid (dtpa); dithiocyclohexanoic acid; dithiofuroic acid; dithionaphthoic acid; phenyl dithioacetate; phenyl dithiopropionate; phenyl dithiobenzoate; phenyl dithiocyclohexanoate; phenyl dithiofuroate; phenyl dithionaphthoate; tetrathiooxalic acid; tetrathiomalonic acid; tetrathiosuccinic acid; trithiooxalic acid; trithiomalonic acid; trithiosuccinic acid; diphenyl tetrathiooxalate; diphenyl tetrathiomalonate; diphenyl tetrathiosuccinate; diphenyl trithiooxalate; diphenyl trithiomalonate; diphenyl trithiosuccinate; pyridine dithiocarboxylic acid; pyrrole dithiocarboxylic acid; thiophene dithiocarboxylic acid; dithionaphthoic acid; and tetrathiocamphonic acid.
[0221] S Valence Stabilizer #29: Examples of perthiomonocarboxylic acids, perthiodicarboxylic acids, bis(perthiomonocarboxylic acids), bis(perthiodicarboxylic acids), poly(perthiomonocarboxylic acids), poly(perthiodicarboxylic acids), and derivatives thereof (S—S Bidentates and S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: perthioacetic acid; perthiopropionic acid; perthiobenzoic acid; perthiophenylacetic acid; perthiocyclohexanoic acid; perthiofuroic acid; perthionaphthoic acid; phenyl perthioacetate; phenyl perthiopropionate; phenyl perthiobenzoate; phenyl perthiocyclohexanoate; phenyl perthiofuroate; phenyl perthionaphthoate; perthiooxalic acid; perthiomalonic acid; perthiosuccinic acid; diphenyl perthiooxalate; diphenyl perthiomalonate; diphenyl perthiosuccinate; dithiole-3-thione (dithione-3-thione); and benzodithiole-3-thione (benzodithione-3-thione).
[0222] S Valence Stabilizer #30: Examples of dithiocarbonates, trithiocarbonates, perthiocarbonates, bis(dithiocarbonates), bis(trithiocarbonates), and bis(perthiocarbonates) (S—S Bidentates and S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: S,S-diethyldithiocarbonate; S,S-diisopropyldithiocarbonate; S,S-diphenyldithiocarbonate; S,S-dibenzyldithiocarbonate; S,S-dicyclohexyldithiocarbonate; S,S-dinorbornyldithiocarbonate; diethyltrithiocarbonate; diisopropyltrithiocarbonate; diphenyltrithiocarbonate; dibenzyltrithiocarbonate; dicyclohexyltrithiocarbonate; and dinorbornyltrithiocarbonate.
[0223] S Valence Stabilizer #31: Examples of dithiocarbamates, bis(dithiocarbamates), and poly(dithiocarbamates) (including N-hydroxydithiocarbamates and N-mercaptodithiocarbamates) (S—S Bidentates, S—S Tridentates, and S—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dimethyldithiocarbamate (dmdtc); di(trifluorodimethyl)dithiocarbamate; diethyldithiocarbamate (dedtc); dipropyldithiocarbamate; diisopropyldithiocarbamate; dibutyldithiocarbamate; ditertbutyldithiocarbamate; dicyanamidodithiocarbamate; azidothioformates; diphenyldithiocarbamate; di(pentafluorophenyl)dithiocarbamate; dibenzyldithiocarbamate; dinaphthyldithiocarbamate; dicyclohexyldithiocarbamate; dinorbornyldithiocarbamate; diadamantyldithiocarbamate; pyrrolidinodithiocarbamate (pyrdtc); piperidinodithiocarbamate (pipdtc); morpholinodithiocarbamate (mordtc); thiamorpholinodithiocarbamate; 3-pyrrolinodithiocarbamate; pyrrolodithiocarbamate; oxazolodithiocarbamate; isoxazolodithiocarbamate; thiazolodithiocarbamate; isothiazolodithiocarbamate; indolodithiocarbamate; carbazolodithiocarbamate; pyrazolinodithiocarbamate; imidazolinodithiocarbamate; pyrazolodithiocarbamate; imidazolodithiocarbamate; indazolodithiocarbamate; and triazolodithiocarbamate.
[0224] S Valence Stabilizer #32: Examples of dithiocarbazates (dithiocarbazides), bis(dithiocarbazates), and poly(dithiocarbazates) (S—S Bidentates, S—S Tridentates, and S—S Tetradentates; or possibly N—S Bidentates, N—S Tridentates, and N—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N,N′-dimethyldithiocarbazate; N,N′-di(trifluoromethyl)dithiocarbazate; N,N′-diethyldithiocarbazate; N,N′-diphenyldithiocarbazate; N,N′-dibenzyldithiocarbazate; N,N′-di(pentafluorophenyl)dithiocarbazate; N,N′-dicyclohexyldithiocarbazate; and N,N′-dinorbornyldithiocarbazate.
[0225] S Valence Stabilizer #33: Examples of thiocyanate ligands (S monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn include, but are not limited to: thiocyanate (—SCN).
[0226] O Valence Stabilizer #1: Examples of biurets (imidodicarbonic diamides), isobiurets, biureas, triurets, triureas, bis(biurets), bis(isobiurets), bis(biureas), poly(biurets), poly(isobiurets), and poly(biureas) (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: biuret, isobiuret, biurea, triuret, triurea, nitrobiuret, dinitrobiuret, aminobiuret, diaminobiuret, oxybiuret, dioxybiuret, cyanobiuret, methylbiuret, ethylbiuret, isopropylbiuret, phenylbiuret, benzylbiuret, cyclohexylbiuret, norbornylbiuret, adamantylbiuret, dimethylbiuret, diethylbiuret, diisopropylbiuret, diphenylbiuret, dibenzylbiuret, dicyclohexylbiuret, dinorbornylbiuret, and diadamantylbiuret.
[0227] O Valence Stabilizer #2: Examples of acylureas, aroylureas, bis(acylureas), bis(aroylureas), poly(acylureas), and poly(aroylureas) (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: formylurea, acetylurea, benzoylurea, cyclohexoylurea, pentafluorobenzoylurea, N-methylacetylurea, N-phenylbenzoylurea, and N-cyclohexylcyclohexoylurea.
[0228] O Valence Stabilizer #3: Examples of imidodialdehydes, hydrazidodialdehydes (acyl hydrazides), bis(imidodialdehydes), bis(hydrazidodialdehydes), poly(imidodialdehydes), and poly(hydrazidodialdehydes) (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diacetamide, dipropanamide, dibutanamide, dibenzamide, and dicyclohexamide.
[0229] O Valence Stabilizer #4: Examples of imidodicarbonic acids, hydrazidodicarbonic acids, bis(imidodicarbonic acids), bis(hydrazidodicarbonic acids), poly(imidodicarbonic acids), poly(hydrazidodicarbonic acids) and derivatives thereof (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: imidodicarbonic acid, hydrazidodicarbonic acid, O-phenylimidodicarbonic acid, O-benzylimidodicarbonic acid, O-cyclohexylimidodicarbonic acid, o-norbornylimidodicarbonic acid, O,O′-diphenylimidodicarbonic acid, O,O′-dibenzylimidodicarbonic acid, O,O′-dicyclohexylimidodicarbonic acid, and O,O′-dinorbornylimidodicarbonic acid.
[0230] O Valence Stabilizer #5: Examples of imidodisulfamic acid, imidodisulfuric acid, bis(imidodisulfamic acid), bis(imidodisulfuric acid), poly(imidodisulfamic acid), and poly(imidodisulfuric acid) and derivatives thereof (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: imidodisulfamic acid, imidodisulfuric acid, N-phenylimidodisulfamic acid, N-benzylimidodisulfamic acid, N-cyclohexylimidodisulfamic acid, N-norbornylimidodisulfamic acid, N,N′-diphenylimidodisulfamic acid, N,N′-dibenzylimidodisulfainic acid, N,N′-dicyclohexylimidodisulfamic acid, and N,N′-norbornylimidodisulfamic acid.
[0231] O Valence Stabilizer #6: Examples of 1,3-diketones (beta-diketonates), 1,3,5-triketones, bis(1,3-diketones), and poly(1,3-diketones), all with a molecular weight greater than 125 (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: hexafluoropentanedione; dibenzoylmethane (1,3-diphenyl-1,3-propanedione); benzoylpinacolone; dicyclohexoylmethane; diphenylpentanetrionate; dibenzoylacetone; benzoylacetylacetone; dibenzoylacetylacetone; tetramethylnonanetrionate; hexafluoroheptanetrionate; trifluoroheptanetrionate; trifluoroacetylcamphor (facam); and 1,3-indandione.
[0232] O Valence Stabilizer #7: Examples of 1,2-diketones (alpha-diketonates), 1,2,3-triketones, tropolonates, o-quinones, bis(1,2-diketones), and poly(1,2-diketones), all with a molecular weight greater than 100 (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: tropolone; 1,2-benzoquinone (o-quinone); di-tert-butyl-1,2-benzoquinone; hexafluoro-1,2-benzoquinone; 1,2-naphthoquinone; 9,10-phenanthroquinone; and 1,2-indandione.
[0233] O Valence Stabilizer #8: Examples of malonamides (malonodiamides), bis(malonamides), and polymalonamides (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: malonamide, N-phenylmalonamide, N-benzylmalonamide, N-pentafluorophenylmalonamide, N-cyclohexylmalonamide, N-norbornylmalonamide, N,N′-diphenylmalonainide, N,N′-dibenzylnalonamide, N,N′-dipentafluorophenylmalonamide, N,N′-dicyclohexylmalonamide, and N,N′-norbornylmalonamide.
[0234] O Valence Stabilizer #9: Examples of 2-acylacetamides, bis(2-acylacetamides), and poly(2-acylacetamides) (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-acetoacetamide, N-phenyl-2-acetoacetamide, N-pentafluorophenyl-2-acetoacetamide, N-benzyl-2-acetoacetamide, N-cyclohexyl-2-acetoacetamide, N-norbornyl-2-acetoacetamide, N-phenyl-2-benzoacetamide, N-pentafluorophenyl-2-pentafluorobenzoacetamide, and N-cyclohexyl-2-cyclohexoacetamide.
[0235] O Valence Stabilizer #10: Examples of monothiodicarbonic diamides, bis(monothiodicarbonic diamides), and poly(monothiodicarbonic diamides) (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: monothiodicarbonic diamide; N-phenylmonothiodicarbonic diamide; N-pentafluorophenylmonothiodicarbonic diamide; N-benzylmonothiodicarbonic diamide; N-cyclohexylmonothiodicarbonic diamide; N-norbornylmonothiodicarbonic diamide; N,N′-diphenylmonothiodicarbonic diamide; N,N′-dipentafluorophenylmonothiodicarbonic diamide; N,N′-dibenzylmonothiodicarbonic diamide; N,N′-dicyclohexylmonothiodicarbonic diamide; and N,N′-dinorbornylmonothiodicarbonic diamide.
[0236] O Valence Stabilizer #11: Examples of monothiodicarbonic acids, bis(monothiodicarbonic acids), poly(monothiodicarbonic acids), and derivatives thereof (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: monothiodicarbonic acid, O-phenylmonothiodicarbonic acid, O-benzylmonothiodicarbonic acid, O-cyclohexylmonothiodicarbonic acid, O-norbornylmonothiodicarbonic acid, O,O′-diphenylmonothiodicarbonic acid, O,O′-dibenzylmonothiodicarbonic acid, O,O′-dicyclohexylmonothiodicarbonic acid, and O,O′-dinorbornylmonothiodicarbonic acid.
[0237] O Valence Stabilizer #12: Examples of trithionic acid, bis(trithionic acid), poly(trithionic acid), and derivatives thereof (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diphenyl trithionate, dipentafluorodiphenyl trithionate, dicyclohexyl trithionate, and dinorbornyl trithionate.
[0238] O Valence Stabilizer #13: Examples of hypophosphoric acids, bis(hypophosphoric acids), and poly(hypophosphoric acids), and derivatives thereof (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: hypophosphoric acid, O-methylhypophosphoric acid, O-isopropylhypophosphoric acid, O-tert-butylhypophosphoric acid, O-phenylhypophosphoric acid, O-pentafluorophenylhypophosphoric acid, O-benzylhypophosphoric acid, O-cyclohexylhypophosphoric acid, O-norbornylhypophosphoric acid, O,O″-dimethylhypophosphoric acid, O,O″-diisopropylhypophosphoric acid, O,O″-di-tert-butylhypophosphoric acid, O,O″-diphenylhypophosphoric acid, O,O″-di-pentafluorophenylhypophosphoric acid, O,O″-dibenzylhypophosphoric acid, O,O″-dicyclohexylhypophosphoric acid, and O,O″-dinorbornylhypophosphoric acid.
[0239] O Valence Stabilizer #14: Examples of hypophosphoramides, bis(hypophosphoramides), and poly(hypophosphoramides) (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: hypophosphoramide, N-methylhypophosphoramide, N-isopropylhypophosphoramide, N-tert-butylhypophosphoramide, N-phenylhypophosphoramide, N-pentafluorophenylhypophosphoramide, N-benzylhypophosphoramide, N-cyclohexylhypophosphoramide, N-norbornylhypophosphoramide, N,N′″-dimethylhypophosphoramide, N,N′″-diisopropylhypophosphoramide, N,N′″-di-tert-butylhypophosphoramide, N,N′″-diphenylhypophosphoramide, N,N′″-di-pentafluorophenylhypophosphoramide, N,N′″-dibenzylhypophosphoramide, N,N′″-dicyclohexylhypophosphoramide, and N,N′″-dinorbornylhypophosphoramide.
[0240] O Valence Stabilizer #15: Examples of imidodiphosphoric acids, hydrazidodiphosphoric acids, bis(imidodiphosphoric acids), bis(hydrazidodiphosphoric acids), poly(imidodiphosphoric acids), poly(hydrazidodiphosphoric acids), and derivatives thereof (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: imidodiphosphoric acid, methylimidodiphosphoric acid, isopropylimidodiphosphoric acid, tert-butylimidodiphosphoric acid, phenylimidodiphosphoric acid, pentafluorophenylimidodiphosphoric acid, benzylimidodiphosphoric acid, cyclohexylimidodiphosphoric acid, norbornylimidodiphosphoric acid, dimethylimidodiphosphoric acid, diisopropylimidodiphosphoric acid, di-tert-butylimidodiphosphoric acid, diphenylimidodiphosphoric acid, di-pentafluorophenylimidodiphosphoric acid, dibenzylimidodiphosphoric acid, dicyclohexylimidodiphosphoric acid, and dinorbornylimidodiphosphoric acid.
[0241] O Valence Stabilizer #16: Examples of imidodiphosphoramides, hydrazidodiphosphoramides, bis(imidodiphosphoramides), bis(hydrazidodiphosphoramides), poly(imidodiphosphoramides), and poly(hydrazidodiphosphoramides) (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: imidodiphosphoramide, N-methylimidodiphosphoramide, N-isopropylimidodiphosphoramide, N-tert-butylimidodiphosphoramide, N-phenylimidodiphosphoramide, N-pentafluorophenylimidodiphosphoramide, N-benzylimidodiphosphoramide, N-cyclohexylimidodiphosphoramide, N-norbornylimidodiphosphoramide, N,N′″-dimethylimidodiphosphoramide, N,N′″-diisopropylimidodiphosphoramide, N,N′″-di-tert-butylimidodiphosphoramide, N,N′″-diphenylimidodiphosphoramide, N,N′″-di-pentafluorophenylimidodiphosphoramide, N,N′″-dibenzylimidodiphosphoramide, N,N′″-dicyclohexylimidodiphosphoramide, and N,N′″-dinorbornylimidodipbosphoramide.
[0242] O Valence Stabilizer #17: Examples of diphosphoramides, bis(diphosphoramides), and poly(diphospboramides) (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diphosphoramide, N-methyldphosphoramide, N-isopropyldiphosphoramide, N-tert-butyldiphosphoramide, N-phenyldiphosphoramide, N-pentafluorophenyldiphosphoramide, N-benzyldiphosphoramide, N-cyclohexyldiphosphoramide, N-norbornyldiphosphoramide, N,N′″-dimethyldiphosphoramide, N,N′″-diisopropyldiphosphoramide, N,N′″-di-tert-butyldiphosphoramide, N,N′″-diphenyldiphosphoramide, N,N′″-di-pentafluorophenyldiphosphoramide, N,N′″-dibenzyldiphosphoramide, N,N′″-dicyclohexyldiphosphoramide, and N,N′″-dinorbornyldiphosphoramide.
[0243] O Valence Stabilizer #18: Examples of beta-hydroxyketones, beta-hydroxyaldehydes, bis(beta-hydroxyketones), bis(beta-hydroxyaldehydes), poly(beta-hydroxyketones), and poly(beta-hydroxyaldehydes) (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+ include, but are not limited to: 4-hydroxypentan-2-one; 1,3-diphenyl-3-hydroxypropanal; 1,3-dibenzyl-3-hydroxypropanal; 1,3-dicyclohexyl-3-hydroxypropanal; 1,3-dinorbornyl-3-hydroxypropanal; 1,3-di(2-thienyl)-3-hydroxypropanal; 1,3-di(2-furyl)-3-hydroxypropanal; o-hydroxyacetophenone; juglone; alizarin; 1-hydroxyanthraquinone; 1,8-hydroxyanthraquinone; 1-hydroxyacridone; and beta-hydroxybenzophenone.
[0244] O Valence Stabilizer #19: Examples of N-(aminomethylol)ureas [N-(aminohydroxymethyl)ureas], bis[N-(aminomethylol)ureas], and poly[N-(aminomethylol)ureas] (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N′-(aminohydroxymethyl)urea; N,N″-dimethyl-N′-(aminohydroxymethyl)urea; N,N′-diethyl-N′-(aminohydroxymethyl)urea; N,N″-isopropyl-N′-(aminohydroxymethyl)urea; N,N″-diphenyl-N′-(aminohydroxymethyl)urea; N,N″-dibenzyl-N′-(aminohydroxymethyl)urea; N,N″-dicyclohexyl-N′-(aminohydroxymethyl)urea; and N,N″-dinorbornyl-N′-(aminohydroxymethyl)urea.
[0245] O Valence Stabilizer #20: Examples of oxamides, bis(oxamides), and poly(oxamides) (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: oxamide, N-methyloxamide; N-ethyloxamide; N-isopropyloxamide; N-phenyloxamide; N-benzyloxamide; N-cyclohexyloxamide; N-norbornyloxamide; N,N′-dimethyloxamide; N,N′-diethyloxamide; N,N′-diisopropyloxamide; N,N′-diphenyloxamide; N,N′-dibenzyloxamide; N,N′-dicyclohexyloxamide; and N,N′-dinorbornyloxamide.
[0246] O Valence Stabilizer #21: Examples of squaric acids and derivatives thereof (O—O Bidentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: deltic acid; squaric acid; croconic acid; and rhodizonic acid.
[0247] O Valence Stabilizer #22: Examples of dicarboxylic acids, bis(dicarboxylic acids), poly(dicarboxylic acids), and derivatives thereof (O—O Bidentates and O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: oxalic acid; malonic acid; succinic acid; diphenyl oxalate; diphenyl malonate; and diphenyl succinate.
[0248] O Valence Stabilizer #23: Examples of carbamates, bis(carbamates), and poly(carbamates) (including N-hydroxycarbamates and N-mercaptocarbamates) (O—O Bidentates, O—O Tridentates, and O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dimethylcarbamate (dmc); di(trifluorodimethyl)carbamate; ethyl carbamate; diethylcarbamate (dec); dipropylcarbamate; diisopropylcarbamate; dibutylcarbamate; ditertbutylcarbamate; dicyanamidocarbamate; diphenylcarbainate; di(pentafluorophenyl)carbamate; dibenzylcarbamate; dinaphthylcaibamate; dicyclohexylcarbamate; dinorbornylcarbamate; diadamantylcarbamate; pyrrolidinocarbamate (pyrc); piperidinocarbamate (pipc); morpholinocarbamate (morc); thiamorpholinocarbamate; 3-pyrrolinocarbamate; pyrrolocarbamate; oxazolocarbamate; isoxazolocarbamate; thiazolocarbamate; isothiazolocarbamate; indolocarbamate; carbazolocarbamate; pyrazolinocarbamate; imidazolinocarbamate; pyrazolocarbamate; imidazolocarbamate; indazolocarbamate; and triazolocarbamate.
[0249] O Valence Stabilizer #24: Examples of carbimates, bis(carbimates), and poly(carbimates) (O—O Bidentates, O—O Tridentates, and O—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: methylcarbimate; trifluoromethylcarbimate; ethylcarbimate; propylcarbimate; isopropylcarbimate; butylcarbimate; tertbutylcarbimate; cyanocarbimate; cyanamidocarbimate; azidocarbimate; phenylcarbimate; pentafluorophenylcarbimate; benzylcarbimate; naphthylcarbimate; cyclohexylcarbimate; norbornylcarbimate; and adamantylcarbimate. [Note: Carbimates tend to stabilize lower oxidation states in metal ions.]
[0250] O Valence Stabilizer #25: Examples of cyanate ligands (O monodentates) that meet the 5 requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: cyanate (—OCN).
[0251] N—S Valence Stabilizer #1: Examples of diformamidine disulfides (thioperoxydicarbonimidic diamides), thioperoxytricarbonimidic diamides, thioperoxytetracarbonimidic diamides, bis(diformamidine disulfides), and poly(diformamidine disulfides) (N—S bidentates, N—N—S tridentates, or N—S tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diformamidine disulfide; methyldiformamidine disulfide; ethyldiformamidine disulfide; isopropyldiformamidine disulfide; butyldiformamidine disulfide; benzyldiformamidine disulfide; phenyldiformamidine disulfide; tolyldiformamidine disulfide; naphthyldiformamidine disulfide; cyclohexyldiformamidine disulfide; norbornyldiformamidine disulfide; adamantyldiformamidine disulfide; dimethyldiformamidine disulfide; diethyldiformamidine disulfide; diisopropyldiformamidine disulfide; dibutyldiformamidine disulfide; dibenzyldiformamidine disulfide; diphenyldiformamidine disulfide; ditolyldiformamidine disulfide; dinaphthyldiformamidine disulfide; dicyclohexyldiformamidine disulfide; dinorbornyldiformamidine disulfide; diadamantyldiformamidine disulfide; 2-S-amidinodisulfidothiazole; 2-S-amidinodisulfidooxazole; 2-S-amidinodisulfidoimidazole; 3-S-amidinodisulfidopyrazole; 3-S-amidinodisulfido-1,2,4-triazole; and 5-S-amidinodisulfidotetrazole.
[0252] N—S Valence Stabilizer #2: Examples of S-amidinodithiocarbamates, bis(S-amidinodithiocarbamates), and poly(S-amidinodithiocarbamates) (N—S Bidentates and N—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: S-amidinodithiocarbamate; N-methyl-S-amidinodithiocarbamate; N-ethyl-S-amidinodithiocarbamate; N-isopropyl-S-amidinodithiocarbamate; N-butyl-S-amidinodithiocarbamate; N-benzyl-S-amidinodithiocarbamate; N-phenyl-S-amidinodithiocarbamate; N-tolyl-S-amidinodithiocarbamate; N-naphthyl-S-amidinodithiocarbamate; N-cyclohexyl-S-amidinodithiocarbamate; N-norbornyl-S-amidinodithiocarbamate; N-adamantyl-S-amidinodithiocarbamate; N,N′-dimethyl-S-amidinodithiocarbamate; N,N′-diethyl-S-amidinodithiocarbamate; N,N′-diisopropyl-S-amidinodithiocarbamate; N,N′-dibutyl-S-amidinodithiocarbamate; N,N′-dibenzyl-S-amidinodithiocarbamate; N,N′-diphenyl-S-amidinodithiocarbamate; N,N′-ditolyl-S-amidinodithiocarbamate; N,N′-dinapbthyl-S-amidinodithiocarbamate; N,N′-dicyclohexyl-S-amidinodithiocarbamate; N,N′-dinorbornyl-S-amidinodithiocarbamate; N,N′-diadamantyl-S-amidinodithiocarbamate; etbylenebis(S-amidinodithiocarbamate); propylenebis(S-amidinodithiocarbamate); phenylenebis(S-amidinodithiocarbamate); piperazinebis(S-amidinodithiocarbamate); oxalylbis(S-amidinodithiocarbamate); malonylbis(S-amidinodithiocarbamate); succinylbis(S-amidinodithiocarbamate); phthalylbis(S-amidinodithiocarbamate); 2-S-dithiocarbamatothiazole; 2-S-dithiocarbamatooxazole; 2-S-dithiocarbamatoimidazole; 3-S-dithiocarbamatopyrazole; 3-S-dithiocarbamato-1,2,4-triazole; and 5-S-dithiocarbamatotetrazole.
[0253] N—S Valence Stabilizer #3: Examples of O-amidinothiocarbamates, bis(O-amidinothiocarbamates), and poly(O-amidinothiocarbamates) (N—S Bidentates and N—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: O-amidinothiocarbamate; N-methyl-O-amidinothiocarbamate; N-ethyl-O-amidinothiocarbamate; N-isopropyl-O-amidinothiocarbamate; N-butyl-O-amidinothiocarbamate; N-benzyl-O-amidinothiocarbamate; N-pbenyl-O-amidinothiocarbamate; N-tolyl-O-amidinothiocarbamate; N-naphthyl-O-amidinothiocarbamate; N-cyclohexyl-O-amidinothiocarbamate; N-norbornyl-O-amidinothiocarbamate; N-adamantyl-O-amidinothiocarbamate; N,N′-dimethyl-O-amidinothiocarbamate; N,N′-diethyl-O-amidinothiocarbamate; N,N′-diisopropyl-O-amidinothiocarbamate; N,N′-dibutyl-O-amdinothiocarbamate; N,N′-dibenzyl-O-amidinothiocarbamate; N,N′-diphenyl-O-amidinothiocarbamate; N,N′-ditolyl-O-amidinothiocarbamate; N,N′-dinaphthyl-O-amidinothiocarbamate; N,N′-di cyclohexyl-O-amidinothiocarbamate; N,N′-dinorbornyl-O-amidinothiocarbamate; N,N′-diadamantyl-O-amidinothiocarbamate; ethylenebis(O-amidinothiocarbamate); propylenebis(O-amidinothiocarbamate); phenylenebis(O-amidinothiocarbamate); piperazinebis(O-amidinothiocarbamate); oxalylbis(O-amidinothiocarbamate); malonylbis(O-amidinothiocarbamate); succinylbis(O-amidinothiocarbamate); phthalylbis(O-amidinothiocarbamate); 2-O-monothiocarbamatothiazole; 2-O-monothiocarbamatooxazole; 2-O-monothiocarbamatoimidazole; 3-O-monothiocarbamatopyrazole; 3-O-monothiocarbamato-1,2,4-triazole; and 5-O-monothiocarbamatotetrazole.
[0254] N—S Valence Stabilizer #4: Examples of S-amidinoperoxythiocarbamates, bis(S-amidinoperoxythiocarbamates), and poly(S-amidinoperoxythiocarbamates) (N—S Bidentates and N—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: S-amidinoperoxythiocarbamate; N-methyl-S-amidinoperoxythiocarbamate; N-ethyl-S-amidinoperoxythiocarbamate; N-isopropyl-S-amidinoperoxythiocarbamate; N-butyl-S-amidinoperoxythiocarbamate; N-benzyl-S-amidinoperoxythiocarbamate; N-phenyl-S-amidinoperoxythiocarbamate; N-tolyl-S-amidinoperoxythiocarbamate; N-naphthyl-S-amidinoperoxythiocarbamate; N-cyclohexyl-S-amidinoperoxythiocarbamate; N-norbornyl-S-amidinoperoxythiocarbamate; N-adamantyl-S-amidinoperoxythiocarbamate; N,N′-dimethyl-S-amidinoperoxythiocarbamate; N,N′-diethyl-S-amidinoperoxythiocarbamate; N,N′-diisopropyl-S-amidinoperoxythiocarbamate; N,N′-dibutyl-S-amidinoperoxythiocarbamate; N,N′-dibenzyl-S-amidinoperoxythiocarbamate; N,N′-diphenyl-S-amidinoperoxythiocarbamate; N,N′-ditolyl-S-amidinoperoxythiocarbamate; N,N′-dinaphthyl-S-amidinoperoxythiocarbamate; N,N′-dicyclohexyl-S-amidinoperoxythiocarbamate; N,N′-dinorbornyl-S-amidinoperoxythiocarbamate; N,N′-diadamantyl-S-amidinoperoxythiocarbamate; ethylenebis(S-amidinoperoxythiocarbamate); propylenebis(S-amidinoperoxythiocarbamate); phenylenebis(S-amidinoperoxythiocarbamate); piperazinebis(S-amidinoperoxythiocarbamate); oxalylbis(S-amidinoperoxythiocarbamate); malonylbis(S-amidinoperoxythiocarbamate); succinylbis(S-amidinoperoxythiocarbamate); and phthalylbis(S-amidinoperoxythiocarbamate).
[0255] N—S Valence Stabilizer #5: Examples of phosphorimidothioic acid; phosphorimidodithioic acid; phosphorimidotrithioic acid; bis(phosphorimidothioic acid); bis(phosphorimidodithioic acid); bis(phosphorimidotrithioic acid); poly(phosphorimidothioic acid); poly(phosphorimidodithioic acid); poly(phosphorimidotrithioic acid); and derivatives thereof (N—S Bidentates and N—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: phosphorimidothioic acid; phosphorimidodithioic acid; phosphorimidotritbioic acid; O-phenylphosphorimidothioic acid; O-benzylphosphorimidothioic acid; O-cyclohexylphosphorimidothioic acid; O-norbornylphosphorimidothioic acid; O,O′-diphenylphosphorimidothioic acid; O,O′-dibenzylphosphorimidothioic acid; O,O′-dicyclohexylphosphorimidothioic acid; and O,O′-dinorbornylphosphorimidothioic acid.
[0256] N—S Valence Stabilizer #6: Examples of phosphorothioic triamides, bis(phosphorothioic triamides), and poly(phosphorothioic triamides) (N—S Bidentates and N—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: phosphorothioic triamide; phosphorothioic trihydrazide; phosphoramidothioic dihydrazide; N-phenylphosphorothioic triamide; N-benzylphosphorothioic triamide; N-cyclohexylphosphorothioic triamide; N-norbornylphosphorothioic triamide; N,N′-diphenylphosphorothioic triamide; N,N′-dibenzylphosphorothioic triamide; N,N′-dicyclohexylphosphorothioic triamide; and N,N′-dinorbornylphosphorothioic triamide.
[0257] N—S Valence Stabilizer #7: Examples of phosphoramidotrithioic acid, phosphorodiamidodithioic acid, bis(phosphoramidotritbioic acid), bis(phosphorodiamidodithioic acid), poly(phosphoramidotrithioic acid), poly(phosphorodiamidodithioic acid), and derivatives thereof (N—S Bidentates and N—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: phosphoramidotrithioic acid, phosphorodiamidodithioic acid, S-phenylphosphoramidotrithioic acid, S-benzylphosphoramidotrithioic acid, S-cyclohexylphosphoramidotrithioic acid, S-norbornylphosphoramidotrithioic acid, S,S′-diphenylphosphoramidotritbioic acid, S,S′-dibenzylphosphoramidotrithioic acid, S,S′-dicyclohexylphosphoramidotrithioic acid, and S,S′-dinorbornylphosphoramidotrithioic acid.
[0258] N—S Valence Stabilizer #8: Examples of phosphoramidothioic acid, phosphoramidodithioic acid, phosphorodiamidothioic acid, bis(phosphoramidothioic acid), bis(phosphoramidodithioic acid), bis(phosphorodiamidothioic acid), poly(phosphoramidothioic acid), poly(phosphoramidodithioic acid), and poly(phosphorodiamidothioic acid) (N—S Bidentates and N—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: phosphoramidothioic acid, phosphoramidodithioic acid, phosphorodiamidothioic acid, phosphorohydrazidothioic acid, phosphorohydrazidodithioic acid, phosphorodihydrazidothioic acid, phosphoramidohydrazidothioic acid, O-phenylphosphoramidothioic acid, O-benzylphosphoramidothioic acid, O-cyclobexylphosphoramidothioic acid, O-norbornylphosphoramidothioic acid, S-phenylphosphoramidodithioic acid, S-benzylphosphoramidodithioic acid, S-cyclohexylphosphoramidodithioic acid, and S-norbornylphosphoramidodithioic acid.
[0259] N—S Valence Stabilizer #9: Examples of N-thioacyl 7-aminobenzylidenimines (N—S Bidentates or N—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N-thioacetyl 7-methylaminobenzylidenimine; N-thioacetyl 7-phenylaminobenzylidenimine; N-thiobenzoyl 7-methylaminobenzylidenimine; and N-thiobenzoyl 7-phenylaminobenzylidenimine.
[0260] N—S Valence Stabilizer #10: Examples of thiohydroxamates (thiohydroxylamines), bis(thiohydroxamates), and poly(thiohydroxamates) (N—S Bidentates, N—S Tetradentates, and N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: acetothiohydroxamic acid; propianothiohydroxamic acid; butyrothiohydroxamic acid; crotonothiohydroxamic acid; sorbothiohydroxamic acid; benzothiohydroxamic acid; toluicthiohydroxamic acid; salicylthiohydroxamic acid; phenylacetothiohydroxamic acid; anthranilthiohydroxamic acid; nicotinethiohydroxamic acid; picolinethiohydroxamic acid; cyclohexanethiohydroxamic acid; quinoline 8-thiohydroxamic acid; cinnamylthiohydroxamic acid; oxaldithiohydroxamic acid; succinylbis-N-phenylthiohydroxamic acid; adipylbis-N-phenylthiohydroxamic acid; glyoxalthiohydroxamic acid; 2-thiophenethiocarbohydroxamic acid; thenoylthiohydroxamic acid; N-phenylbenzothiohydroxamic acid; N-tolylbenzothiohydroxamic acid; N-phenylacetothiohydroxamic acid; N-phenyl-2-thenoylthiohydroxamic acid; and N-tolyl-2-thenoylthiohydroxamic acid.
[0261] N—S Valence Stabilizer #11: Examples of alpha- or ortho-aminothiocarboxylic acids, and alpha- or ortho-aminothiodicarboxylic acids, and derivatives thereof (N—S Bidentates, N—S Tridentates, and N—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-pyridinethiocarboxylic acid (thiopicolinic acid); 2-pyrazinethiocarboxylic acid; o-aminothiobenzoic acid; o-aminothionaphthoic acid; and 3,6-diaminothiophthalic acid.
[0262] N—S Valence Stabilizer #12: Examples of thiosemicarbazones, bis(thiosemicarbazones), and poly(thiosemicarbazones) (N—S Bidentates, N—S Tetradentates, and N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: acetaldehyde thiosemicarbazone; acetone thiosemicarbazone; pinacolone thiosemicarbazone; benzaldehyde thiosemicarbazone; naphthaldehyde thiosemicarbazone; norbornanone thiosemicarbazone; camphor thiosemicarbazone; nopinone thiosemicarbazone; 2-pyridinaldehyde thiosemicarbazone; salicylaldehyde thiosemicarbazone; quinolinaldehyde thiosemicarbazone; isatin dithiosemicarbazone; camphorquinone dithiosemicarbazone; camphorquinone dithiosemicarbazone; picolinaldehyde thiosemicarbazone; dipyridyl glyoxal dithiosemicarbazone; di-2-pyridyl ketone thiosemicarbazone; methyl-2-pyridyl ketone thiosemicarbazone; glyoxal dithiosemicarbazone; acetophenone thiosemicarbazone; biacetyl monoxime thiosemicarbazone; acetamidobenzaldehyde thiosemicarbazone; thymolaldothiosemicarbazone; thiophene-2-aldehyde thiosemicarbazone; phthalaldehyde dithiosemicarbazone; phthalimide dithiosemicarbazone; furaldehyde thiosemicarbazone; naphthoquinone thiosemicarbazone; phenanthrequinone thiosemicarbazone; cyclohexanedione dithiosemicarbazone; ionone thiosemicarbazone; bisthiosemicarbazone of diethyl-3,4-dioxadioate; pyridoxal alkylthiosemicarbazones; benzylidene phenylthiosemicarbazones; lawsone thiosemicarbazone; and 1-benzoin-4-phenylthiosemicarbazone (bps).
[0263] N—S Valence Stabilizer #13: Examples of thioacyl hydrazones, bis(thioacyl hydrazones), and poly(thioacyl hydrazones) (N—S Bidentates, N—S Tetradentates, and N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: acetaldehyde N-thioformylhydrazone; acetaldehyde N-thiobenzoylhydrazone; acetone N-thioformylhydrazone; acetone N-thiobenzoylhydrazone; pinacolone N-thioformylhydrazone; pinacolone N-thiobenzoylhydrazone; benzaldehyde N-thioformylhydrazone; benzaldehyde N-thiobenzoylhydrazone; naphthaldehyde N-thioformylhydrazone; naphthaldehyde N-thiobenzoylhydrazone; norbornanone N-thioformylhydrazone; norbornanone N-thiobenzoylhydrazone; camphor N-thioformylhydrazone; camphor N-thiobenzoylhydrazone; nopinone N-thioformylhydrazone; nopinone N-thiobenzoylhydrazone; 2-pyridinaldehyde N-thioformylhydrazone; 2-pyridinaldehyde N-thiobenzoylhydrazone; salicylaldehyde N-thioformylhydrazone; salicylaldehyde N-thiobenzoylhydrazone; quinolinaldehyde N-thioformylhydrazone; quinolinaldehyde N-thiobenzoylhydrazone; thiophene-2-aldehyde N-thioformylhydrazone; thiophene-2-aldehyde N-thiobenzoylhydrazone; naphthoqui none N-thioformylhydrazone; naphthoqui none N-thiobenzoylhydrazone; ionone N-thioformylhydrazone; ionone N-thiobenzoylhydrazone; benzaldehyde benzothiazolehydrazone; lawsone N-thioformylhydrazone; and lawsone N-thiobenzoylhydrazone.
[0264] N—S Valence Stabilizer #14: Examples of thiocarbazones (diazenecarbothioic hydrazides), bis(thiocarbazones), and poly(thiocarbazones) (N—S Bidentates, N—S Tetradentates, and N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diphenylthiocarbazone (dithizone); 2-phenylthiocarbazone; dinaphthylthiocarbazone; 2-naphthylthiocarbazone; and ambazone.
[0265] N—S Valence Stabilizer #15: Examples of azo compounds with thiol or mercapto or thiocarbonyl substitution at the ortho- (for aryl) or alpha- or beta- (for alkyl) positions, Bis[o-(HS—) or alpha- or beta-(HS—)azo compounds], or Poly[o-(HS—) or alpha- or beta-(HS—)azo compounds) (N—S Bidentates, N—S Tridentates, N—S Tetradentates, or N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-thiolazobenzene [1-(phenylazo)-2-thiophenol]; 2,2′-dithioazobenzene; (2-thiophene)azobenzene; 1-(4-nitrophenylazo)-2-thionaphthol; 2-thiazolylazobenzene; and 2-benzothiazolylazobenzene.
[0266] N—S Valence Stabilizer #16: Examples of diazeneformothioamides, diazeneacetothioamides, bis(diazeneformothioamides), bis(diazeneacetothioamides), poly(diazeneformothioamides), and poly(diazeneacetothioamides) (N—S Bidentates, N—S Tetradentates, and N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diazeneformothioamide, diazeneacetothioamide, phenyldiazeneformothioamide, diphenyldiazeneformothioamide, phenyldiazeneacetothioamide, and diphenyldiazeneacetothioamide.
[0267] N—S Valence Stabilizer #117: Examples of diazenecarbothioic acids, diazenecarbodithioic acids, bis(diazenecarbothioic acids), bis(diazenecarbodithioic acids), poly(diazenecarbothioic acids), poly(diazenecarbodithioic acids) and derivatives thereof (N—S Bidentates, N—S Tetradentates, N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diazeneformothioic acid, diazeneacetothioic acid, phenyldiazeneformothioic acid, diphenyldiazeneformothioic acid, phenyldiazeneacetothioic acid, and diphenyldiazeneacetothioic acid.
[0268] N—S Valence Stabilizer #18: Examples of diazeneformothioaldehydes, diazeneacetothioaldehydes, bis(diazeneformothioaldehydes), bis(diazeneacetothioaldehydes), poly(diazeneformothioaldehydes), and poly(diazeneacetothioaldehydes) (N—S Bidentates, N—S Tetradentates and N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diazeneformothioaldehyde, diazeneacetothioaldehyde, phenyldiazeneformothioaldehyde, diphenyldiazeneformothioaldehyde, phenyldiazeneacetothioaldehyde, and diphenyldiazeneacetothioaldehyde.
[0269] N—S Valence Stabilizer #19: Examples of diazenediformothioamides, diazenediacetothioamides, bis(diazenediformothioamides), bis(diazenediacetothioamides), poly(diazenediformothioamides), and poly(diazenediacetothioamides) (N—S Tridentates and N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diazenediformodithioamide, diazenediacetodithioamide, diphenydiazenediformodithioamide, tetraphenyldiazenediformodithioamide, diphenyldiazenediacetodithioamide, and tetraphenyldiazenediacetodithioamide.
[0270] N—S Valence Stabilizer #20: Examples of diazenedicarbothioic acids, diazenedicarbodithioic acids, bis(diazenedicarbothioic acids), bis(diazenedicarbodithioic acids), poly(diazenedicarbothioic acids), poly(diazenedicarbodithioic acids) and derivatives thereof (N—S Tridentates and N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diazenediformothioic acid, diazenediacetodithioic acid, phenyldiazenediformothioic acid, diphenyldiazenediformothioic acid, phenyldiazenediacetodithioic acid, and diphenyldiazenediacetodithioic acid.
[0271] N—S Valence Stabilizer #21: Examples of diazenediformothioaldehydes, diazenediacetothioaldehydes, bis(diazenediformothioaldehydes), bis(diazenediacetothioaldehydes), poly(diazenediformothioaldehydes), and poly(diazenediacetothioaldehydes) (N—S Tridentates and N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diazenediformothioaldehyde, diazenediacetothioaldehyde, diphenyldiazenediformothioaldehyde, and diphenyldiazenediacetothioaldehyde.
[0272] N—S Valence Stabilizer #22: Examples of ortho-thio (or -mercapto) substituted formazans, bis(o-thio or -mercapto substituted formazans), and poly(o-thio or -mercapto substituted formazans) (N—S Bidentates, N—S Tridentates, N—S Tetradentates, and N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 1-(2-thiophenyl)-3,5-diphenylformazan; 1-(2-methylmercaptophenyl)-3,5-diphenylformazan; 1,5-bis(2-thiophenyl)-3-phenylformazan; and 5-bis(2-methylmercaptophenyl)-3-phenyl formazan.
[0273] N—S Valence Stabilizer #23: Examples of ortho-thio (or -mercapto) substituted azines (including ketazines), bis(o-thio or mercapto substituted azines), and poly(o-thio or mercapto substituted azines) (N—S Bidentates, N—S Tridentates, N—S Tetradentates, and N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-mercapto-1-benzalazine; 2-mercapto-1-naphthalazine; and 2-mercapto-1-cyclohexanonazine.
[0274] N—S Valence Stabilizer #24: Examples of Schiff Bases with one Imine (C═N) Group and with ortho- or alpha- or beta-thio or mercapto or thiocarbonyl substitution (N—S Bidentates, N—S Tridentates, N—S Tetradentates, N—S Pentadentates, or N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N-(Thiosalicylaldehydo)isopropylamine; N-(2-thiophenecarboxaldehydo)isopropylamine; N-(2-Acetylthiopheno)isopropylamine; N-(2-Thioacetophenono)isopropylamine; N-(Thiosalicylaldehydo)cyclohexylamine; N-(2-Thiophenecarboxaldehydo)cyclohexylamine; N-(2-Acetylthiopheno)cyclohexylamine; N-(2-Thioacetophenono)cyclohexylamine; N-(Thiosalicylaldehydo)aniline; N-(2-Thiophenecarboxaldehydo)aniline; N-(2-Acetylthiopheno)aniline; N-(2-Thioacetophenono)aniline; N-(Thiosalicylaldehydo)aminonorbornane; N-(2-Thiocarboxaldehydo)aminonorbornane; N-(2-Acetylthiopheno)aminonorbornane; N-(2-Thioacetophenono)aminonorbornane; 4-aminobenzylidene-3-propyl-5-mercapto-1,2,4-triazole; 4-aminocinnamalidene-3-propyl-5-mercapto-1,2,4-triazole (acpmt); 4-aminosalicylidene-3-propyl-5-mercapto-1,2,4-triazole (aspmt); 4-aminovanillidene-3-propyl-5-mercapto-1,2,4-triazole; 4-aminodimethylaminobenzylidene-3-propyl-5-mercapto-1,2,4-triazole (adpmt); cinnamylideneaminophenylthiazole; N-(2-mercaptophenyl)salicylidenimine; 2-thiophenecarboxaldehyde phenylhydrazone; 2-thiophenecarboxaldehyde 2-pyridyl hydrazone; 2-mercaptobenzaldehyde phenylhydrazone; and 2-mercaptobenzaldehyde 2-pyridyl hydrazone. Also includes Schiff Bases derived from the reaction of carbonyl compounds with dithiocarbazates, and hydrazones with ortho-S substitution.
[0275] N—S Valence Stabilizer #25: Examples of Schiff Bases with two Imine (C═N) Groups and with ortho- or alpha- or beta-thio or mercapto or thiocarbonyl substitution (N—S Tridentates, N—S Tetradentates, N—S Pentadentates, or N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N,N′-(2,5-Thiophenedicarboxaldehydo)diisopropylamine; N,N′-(2,5-Thiophenedicarboxaldehydo)dicyclohexylamine; N,N′-(2,5-Thiophenedicarboxaldehydo)dianiline; N,N′-(2,5-Thiophenedicarboxaldehydo)di-aininonorbornane; N,N′-(o-Thiophthalicdialdehydo)diisopropylamine; N,N′-(o-Thiophthalicdialdehydo)dicyclohexylamine; N,N′-(o-Thiophthalicdialdehydo)dianiline; N,N′-(o-Thiophthalicdialdehydo)di-aminonorbornane; N,N′-(o-Thioformylcamphoro)diisopropylamine; N,N′-(o-Thioformylcamphoro)dicyclohexyl amine; N,N′-(o-Thioformylcamphoro)dianiline; N,N′-(o-Thioformylcamphoro)di-aminonorbornane; N,N′-(o-Thiodiacetylbenzeno)diisopropylamine; N,N′-(o-Thiodiacetylbenzeno)dicyclohexylamine; N,N′-(o-Thiodiacetylbenzeno)dianiline; N,N′-(o-Thiodiacetylbenzeno)di-aminonorbornane; N,N′-(3,6-Dithio-1,2-cyclohexanono)diisopropylamine; N,N′-(3,6-Dithio-1,2-cyclohexanono)dicyclohexylamine; N,N′-(3,6-Dithio-1,2-cyclohexanono)dianiline; N,N′-(3,6-Dithio-1,2-cyclohexanono)di-aminonorbornane; N,N′-(2,5-Diacetylthiopheno)diisopropylamine; N,N′-(2,5-Diacetylthiopheno)dicyclohexylamine; N,N′-(2,5-Diacetylthiopheno)dianiline; N,N′-(2,5-Diacetylthiopheno)di-aminonorbornane; N,N′-(Thiosalicylaldehydo)ethylenediamine; N,N′-(o-Thionaphthaldehydo)ethylenediamine; N,N′-(o-Thioacetophenono)ethylenediamine; N,N′-(Thiosalicylaldehydo)trimethylenediamine; N,N′-(o-Thionaphthaldehydo)trimethylenediamine; N,N′-(o-Thioacetophenono)trimethylenediamine; N,N′-(Thiosalicylaldehydo)cyclohexane-1,2-diamine; N,N′-(o-Thionaphthaldehydo)cyclohexane-1,2-diamine; N,N′-(o-Thioacetophenono)cyclohexane-1,2-diamine; N,N′-(Thiosalicylaldehydo 1,2-diaminobenzene; N,N′-(o-Thionaphthaldehydo)-1,2-diaminobenzene; and N,N′-(o-Thioacetophenono)-1,2-diaminobenzene. Also includes Schiff Bases derived from the reaction of carbonyl compounds with dithiocarbazates, and hydrazones with ortho-S substitution.
[0276] N—S Valence Stabilizer #26: Examples of Schiff Bases with three Imine (C═N) Groups and with ortho- or alpha- or beta-thio or mercapto or thiocarbonyl substitution (N—S Tetradentates, N—S Pentadentates, or N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N,N′,N″-(Thiosalicylaldehydo)tris(2-aminoethyl)amine; N,N′,N″-(o-Thionaphthaldehydo)tris(2-aminoethyl)amine; and N,N′,N″-(o-Thioacetopbenono)tris(2-aminoethyl)amine. Also includes Schiff Bases derived from the reaction of carbonyl compounds with dithiocarbazates, and hydrazones with ortho-S substitution.
[0277] N—S Valence Stabilizer #27: Examples of thioalkyl amines (aminothiols or aminodisulfides) and thioalkyl imines (iminothiols or iminodisulfides) (N—S Bidentates, N—S Tridentates, N—S Tetradentates, and N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-mercapto-1-aminoethane; 2-methylmercapto-1-aminoethane; 3-mercapto-1-aminopropane; 1-mercapto-2-amino-2-methylpropane; 2-mercaptocyclohexylamine; 3-mercapto-2-aminonorbornane; 1,3-dimercapto-2-aminopropane; 1,5-dimercapto-3-aminopentane; 2,2′-diaminodiethyl sulfide; 3,3′-diaminodipropyl sulfide; 2,2′-diaminodicyclohexyl sulfide; 1,6-dimercapto-3,4-diaminohexane; 1,7-dimercapto-3,5-diaminoheptane; 1,6-diamino-3,4-dimercaptohexane; 1,7-diamino-3,5-dimercaptoheptane; tri(mercaptomethyl)amine; tri(2-mercaptoethyl)amine; dithiooxamide (rubeanic acid); 2,2′-diaminodiethyl disulfide; 3,3′-diaminodipropyl disulfide; 2,2′-diaminodicyclohexyl disulfide; 3-amino-1,5-pentanedithiodialdehyde; 3,4-diamino-1,6-hexanedithiodialdehyde; 3,5-diamino-1,7-heptanedithiodialdehyde; iminobisacetic acid; iminobispropionic acid; and bis(hydroxyethyl)aminoalkyl sulfide.
[0278] N—S Valence Stabilizer #28: Examples of thioaryl amines and thioaryl imines (N—S Bidentates, N—S Tridentates, N—S Tetradentates, and N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-aminothiophenol (2-aminobenzenethiol); 2-aminothiobenzoic acid (thioanthranilic acid); 2-aminothioanisole; 2-(methanamine)benzyl mercaptan [(2-aminomethyl)-alpha-toluenethiol] [(2-mercaptomethyl)-alpha-aminotoluene]; 1-amino-2-naphthalenethiol; 2-amino-1-naphthalenethiol; 2-amino-1-(methyldisulfido)benzene; 2,2′-di(aminomethyl)diphenylthioketone; di(2-amino)phenyl sulfide; di(2-amino)phenyl disulfide (di-ortho-aminophenyl disulfide (doapd)); 1,3-di(2-amino)phenyl-2-mercaptopropane; 1,3-di(3-amino)phenyl-2-mercaptopropane; 1,3-di(2-mercapto)phenyl-2-aminopropane; 1,3-di(3-mercapto)phenyl-2-aminopropane; 2,2′-dimercaptoiminodibenzyl; 2,2′-iminodibenzothioic acid; 2,2′-dimercaptoiminostilbene; and poly(o-aminothiophenol).
[0279] N—S Valence Stabilizer #29: Examples of five-membered heterocyclic rings containing one, two, three, or four nitrogen atoms at least one additional sulfur atom binding site not in a ring (N—S Bidentates, N—S Tridentates, N—S Tetradentates, or N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-mercaptopyrrole; 2-(methylthio)methylpyrrole; 2,5-(thiomethyl)pyrrole; 2,5-(methylthiomethyl)pyrrole; 2,6(methyldisulfidomethyl)pyrrole; imidazoline-2-thione (2-mercaptoimidazole); 2-mercaptothiazoline; 2-mercaptobenzimidazole; 2-mercaptobenzothiazole; 2-mercaptobenzoxazole; 2-thiohydantoin; di-2-pyridylthioglyoxal (2,2′-thiopyridil); bis((1-pyrazolyl)methane)sulfide; bis((1-pyrazolyl)methane)disulfide; bis(2-(1-pyrazolyl)ethane)sulfide; bis(2-(1-pyrazolyl)ethane)disulfide; bis(benzimidazolylmethane)sulfide; bis(benzimidazolylethane)sulfide; bis(benzimidazolylmethane)disulfide; bis(benzimidazolylethane)disulfide; tris(imidazolyl)methanethiol; tris(imidazolylmethane)methanethiol; N-thiomethyl-N,N-(benzimidazolylmetbane)amine; N-(2-thioethyl)-N,N-(benzimidazolylmethane)amine; N,N′-di(benzimidazolylmethane)-1,3-diamino-2-mercaptopropane; N,N,N′,N′-tetrakis(benzimidazolylmethane)-1,3-diamino-2-mercaptopropane; bis(N,N-((4-imidazolyl)methane)2-aminoethane)sulfide; bis(N,N-((4-imidazolyl)methane)2-aminoethane)disulfide; 2-aminobenzothiazole (abt); 2-phenylaminothiazole; thiohydantoin; thioxohydropyrazole; 2-mercaptobenzothiazole (mbt); 2-mercapto-1,3,4-thiadiazole; 2,5-dimercapto-1,3,4-thiadiazole (bismuthiol); 2,5-bis(alkylthio)-1,3,4-thiadiazole; 2-amino-5-mercapto-1,3,4-thiadiazole (amt); 5-mercaptotetrazole; 1-phenyl-5-mercaptotetrazole (pmt)(5-mptt); 5-mercaptotriazole; 3-mercaptotriazole; (2-benzothiazolyl)thioacetic acid; (2-benzothiazolyl)thiopropionic acid; (alkylthio)benzotriazoles; (arylthio)benzotriazoles; 2-mercaptopyrimidine; bis(5-mercapto-1,2,4-triazol-3-yl); bis(5-mercapto-1,2,4-triazol-3-yl)alkanes; 2-aminothiazolidine; thiazolidine-2-thione; 2-mercaptothiazolidine; 1-(2-mercaptoethyl)imidazoline; imidazolidine-2-thione; 4,5-dihydroxyimidazolidine-2-thione; 4-amino-5-mercapto-1,2,4-triazole; (2-benzimidazolylthio)carboxylic acids; (2-benzoxazolylthio)carboxylic acids; (2-benzothiazolylthio)carboxylic acids; (2-benzimidazolylthio)hydroxyalkyl(aryl)s; (2-benzoxazolylthio)hydroxyalkyl(aryl)s; (2-benzothiazolylthio) hydroxyalkyl(aryl)s; 2-(phenylmethylthio)benzothiazole; 2,5-bis(hydrocrarbyldithio 1,3,4-thiadiazoles; 2-(hydroarbyldithio)-5-mercapto-1,3,4-thiadiazoles; bis(dithiobi sthiadiazole); benzothi azolethione; 3-hydrazino-5-thio-1,2,4-triazole; imidazolidine-2,4-dithione; dimercaptobenzothi azole; 2-aminothiazole (atz); thiadiazole-2-thione; 5-mercaptothiadiazole-2-thione; 1,1-thiocarbonyldiimidazole; phosphosphonomethylenethio-1,3-benzothiazole (pmtbt); 4,5-dihydroxyimidazolidine-2-thione; imidazolidine-2-thione; 1,1′-thiocarbonyldiimidazole; 2,2′-dithiobis(benzothiazole); and 5,5′-dithiobis(tetrazole).
[0280] N—S Valence Stabilizer #30: Examples of six-membered heterocyclic rings containing one, two, three, or four nitrogen atoms at least one additional sulfur atom binding site not in a ring (N—S Bidentates, N—S Tridentates, N—S Tetradentates, or N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 4-aminomethyl-3-pyridinemethanethiol (including thiopyridoxamine); 2-mercaptopyridine; 2-(methylthio)methylpyridine; 2-(2-(methylthio)ethyl)pyridine; 2,6-(thiomethyl)pyridine; 2,6-(methylthiomethyl)pyridine; 2,6-(methyldisulfidomethyl)pyridine; 2-mercaptopyrimidine; 2-dithiomethylpyrimidine; 2-mercaptoquinoline; 8-mercaptoquinoline (thioxine); 8-methylthioquinoline; 2-mercaptoquinazoline; thioorotic acid (1,2,3,6-tetrahydro-2,6-dithiono-4-pyrimidinecarboxylic acid) (6-thiouracilcarboxylic acid); 1-methylpyrimidine-2-thione; 2-thiouracil; 2,4-dithiouracil; 6-mercaptopurine; bis(N,N,N′,N′-tetra(2-(2-pyridyl)ethane)aminomethane)sulfide; bis(N,N,N′,N′-tetra(2-(2-pyridyl)ethane)aminomethane)disulfide; bis(N,N,N′,N′-tetra(2-(2-pyridyl)ethane)aminoethane)sulfide; bis(N,N,N′,N′-tetra(2-(2-pyridyl)ethane)aminoethane)disulfide; 1,3,5-triazine-6-thione; 2-benzylmercapto-1,3,5-triazine; triazine dithiols [i.e. 6-(phenylamino)-1,3,5-triazine-2,4-dithiol (ptd); 6-aniline-1,3,5-triazine-2,4-dithiol (atd); and 2-(N,N-dialkylamino)-1,3,5-triazine-4,6-dithiol]; 2-thioquinazoline; 2-thioquinazolin-4-one; thiomorpholin-3-thione; [2-(aminomethyl)thio]pyridine; 6-mercaptopurine; dithiouracil; and 2,2′-dithiodipyridine (2,2′-dipyridyl disulfide).
[0281] N—S Valence Stabilizer #31: Examples of five-membered heterocyclic rings containing one or two sulfur atoms at least one additional nitrogen atom binding site not in a ring (N—S Bidentates, N—S Tridentates, N—S Tetradentates, or N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-aminothiophene; 2,5-diaminothiophene; 2-aminomethylthiophene; 2,5-di(aminomethyl)thiophene; 2-aminobenzothiophene; and 2-iminothiolane.
[0282] N—S Valence Stabilizer #32: Examples of six-membered heterocyclic rings containing one or two sulfur atoms at least one additional nitrogen atom binding site not in a ring (N—S Bidentates, N—S Tridentates, N—S Tetradentates, or N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-aminothiopyran; 2,6-diaminothiopyran; 2-aminomethylthiopyran; 2,6-di(aminomethyl)thiopyran; and 2-aminobenzothiopyran.
[0283] N—S Valence Stabilizer #33: Examples of five-membered heterocyclic rings containing one, two, three, or four nitrogen atoms at least one additional sulfur atom binding site in a separate ring (N—S Bidentates, N—S Tridentates, N—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-(2-thiophene)pyrrole; 2,5-di(2-thiophene)pyrrole; 2-(2-thiopyran)pyrrole; 2,5-di(2-thiopyran)pyrrole; 2,5-di(2-pyrrole)thiophene; 2,6-di(2-pyrrole)thiopyran; and 3,5-bis(2-thienyl)-4-amino-1,2,4-triazole (2-tat).
[0284] N—S Valence Stabilizer #34: Examples of six-membered heterocyclic rings containing one, two, three, or four nitrogen atoms at least one additional sulfur atom binding site in a separate ring (N—S Bidentates, N—S Tridentates, N—S Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-(2-thiadiazolyl)benzimidazole; 2-(2-thiophene)pyridine; 2,6-di(2-thiophene)pyridine; 2-(2-thiopyran)pyridine; 2,6di(2-thiopyran)pyridine; 2,5-di(2-pyridyl)thiophene; 2,6-di(2-pyridyl)thiopyran; and 2-(4-thiazolyl)benzimidazole.
[0285] N—S Valence Stabilizer #35: Examples of two-, three-, four-, six-, eight-, and ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen (usually amine or imine groups) or sulfur (usually thiols, mercaptans, or thiocarbonyls) and are not contained in component heterocyclic rings (N—S Bidentates, N—S Tridentates, N—S Tetradentates, and N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: azathiacyclobutane ([4]aneNS); azathiacyclopentane ([5]aneNS); azathiacyclohexane ([6]aneNS); azathiacycloheptane ([7]aneNS); azathiacyclooctane ([8]aneNS); azathiacyclobutene ([4]eneNS); azathiacyclopentene ([5]eneNS); azathiacyclohexene ([6]eneNS); azathiacycloheptene ([7]eneNS); azathiacyclooctene ([8]eneNS); azathiacyclobutadiene ([4]dieneNS); azathiacyclopentadiene ([5]dieneNS); azathiacyclohexadiene ([6]dieneNS); azathiacycloheptadiene ([7]dieneN S); azathiacyclooctadiene ([8]dieneNS); diazathiacyclohexane ([6]aneSN2); diazathiacycloheptane ([7]aneSN2); diazathiacyclooctane ([8]aneSN2); diazathiacyclononane ([9]aneSN2); diazathiacyclodecane ([10]aneSN2); diazathiacycloundecane ([11]aneSN2); diazathiacyclododecane ([12]aneSN2); diazathiacyclohexene ([6]eneSN2); diazathiacycloheptene ([7]eneSN2); diazathiacyclooctene ([8]eneSN2); diazathiacyclononene ([9]eneSN2); diazathiacyclodecene ([10]eneSN2); diazathiacycloundecene ([11]eneSN2); diazathiacyclododecene ([12]eneSN2); diazadithiacyclooctane ([8]aneS2N2); diazadithiacyclononane ([9]aneS2N2); diazadithiacyclodecane ([10]aneS2N2); diazadithiacycloundecane ([11]aneS2N2); diazadithiacyclododecane ([12]aneS2N2); diazadithiacyclotridecane ([13]aneS2N2); diazadithiacyclotetradecane ([14]aneS2N2); diazadithiacyclopentadecane ([15]aneS2N2); diazadithiacyclohexadecane ([16]aneS2N2); diazadithiacycloheptadecane ([17]aneS2N2); diazadithiacyclooctadecane ([18]aneS2N2); diazadithiacyclononadecane ([19]aneS2N2); diazadithiacycloeicosane ([20]aneS2N2); diazadithiacyclooctadiene ([8]dieneS2N2); diazadithiacyclononadiene ([9]dieneS2N2); diazadithiacyclodecadiene ([10]dieneS2N2); diazadithiacycloundecadiene ([11]dieneS2N2); diazadithiacyclododecadiene ([12]dieneS2N2); diazadithiacyclotridecadiene ([13]dieneS2N2); diazadithiacyclotetradecadiene ([14]dieneS2N2); diazadithiacyclopentadecadiene ([15]dieneS2N2); diazadithiacyclohexadecadiene ([16]dieneS2N2); diazadithiacycloheptadecadiene ([17]dieneS2N2); diazadithiacyclooctadecadiene ([18]dieneS2N2); diazadithiacyclononadecadiene ([19]dieneS2N2); diazadithiacycloeicosadiene ([20]dieneS2N2); and tetramethyldithiahexaazacyclobidecanehexaene (mtab).
[0286] N—S Valence Stabilizer #36: Examples of four-, six-, eight-, or ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen or sulfur and are contained in component heterocyclic rings (N—S Bidentates, N—S Tridentates, N—S Tetradentates, or N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiopyrandipyridines; dithiophenedipyrroles; trithiopyrantripyridines; trithiophenetripyrroles; tetrathiopyrantetrapyridines; and tetrathiophenetetrapyrroles.
[0287] N—S Valence Stabilizer #37: Examples of four-, six-, eight-, or ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen or sulfur and are contained in a combination of heterocyclic rings and amine, imine, thiol, mercapto, or thiocarbonyl groups (N—S Bidentates, N—S Tridentates, N—S Tetradentates, or N—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: azathiatetraphyrins; diazadithiatetraphyrins; azathiahexaphyrins; diazadithiahexaphyrins; and triazatrithiahexaphyrins.
[0288] N—O Valence Stabilizer #1: Examples of N-hydroxy (or N,N′-dihydroxy)amidines and N-hydroxy (or N,N′-dihydroxy)diamidines (N—O bidentates, N—O tridentates, or N—O tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N-hydroxy-N,N′-dimethylfonmamidine; N-hydroxy-N,N′-diethylformamidine; N-hydroxy-N,N′-diisopropylformamidine; N-hydroxy-N,N′-dibutylfonmamidine; N-hydroxy-N,N′-diphenylformamidine; N-hydroxy-N,N′-dibenzylformamidine; N-hydroxy-N,N′-dinaphthylformamidine; N-hydroxy-N,N′-dicyclohexylformamidine; N-hydroxy-N,N′-dinorbornylformamidine; N-hydroxy-N,N′-diadamantylformamidine; N-hydroxy-N,N′-dianthraquinonylformamidine; N-hydroxy-N,N′-dimethylacetamidine; N-hydroxy-N,N′-diethylacetamidine; N-hydroxy-N,N′-diisopropylacetamidine; N-hydroxy-N,N′-dibutylacetamidine; N-hydroxy-N,N′-diphenylacetamidine; N-hydroxy-N,N′-dibenzylacetamidine; N-hydroxy-N,N′-dinaphthylacetamidine; N-hydroxy-N,N′-dicyclohexylacetamidine; N-hydroxy-N,N′-dinorbornylacetamidine; N-hydroxy-N,N′-diadamantylacetamidine; N-hydroxy-N,N′-dimethylbenzamidine; N-hydroxy-N,N′-diethylbenzamidine; N-hydroxy-N,N′-diisopropylbenzamidine; N-hydroxy-N,N′-dibutylbenzamidine; N-hydroxy-N,N′-diphenylbenzamidine; N-hydroxy-N,N′-dibenzylbenzamidine; N-hydroxy-N,N′-dinaphthylbenzamidine; N-hydroxy-N,N′-dicyclohexylbenzamidine; N-hydroxy-N,N′-dinorbornylbenzamidine; N-hydroxy-N,N′-diadamantylbenzamidine; N-hydroxy-N,N′-dimethyltoluamidine; N-hydroxy-N,N′-diethyltoluamidine; N-hydroxy-N,N′-diisopropyltoluamidine; N-hydroxy-N,N′-dibutyltoluamidine; N-hydroxy-N,N′-diphenyltoluamidine; N-hydroxy-N,N′-dibenzyltoluamidine; N-hydroxy-N,N′-dinaphthyltoluamidine; N-hydroxy-N,N′-dicyclohexyltoluamidine; N-hydroxy-N,N′-dinorbornyltoluamidine; N-hydroxy-N,N′-diadamantyltoluamidine; N,N-dihydroxyoxalic diamidine; N,N′-dihydroxymalonic diamidine; N,N′-dihydroxysuccinic diamidine; N,N′-dihydroxyglutaric diamidine; N,N′-dihydroxyadipic diamidine; N,N′-dihydroxypimelic diamidine; N,N′-dihydroxysuberic diamidine; N,N′-dihydroxyphthalic diamidine; N,N′-dihydroxyterephthalic diamidine; N,N′-dihydroxyisophthalic diamidine; N,N′-dihydroxypiperazine diamidine.
[0289] N—O Valence Stabilizer #2: Examples of guanylureas, guanidinoureas, bis(guanylureas), bis(guanidinoureas) poly(guanylureas), and poly(guanidinoureas) (N—O Bidentates and N—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: guanylurea (amidinourea)(dicyandiamidine); guanidinourea; methylguanylurea; ethylguanylurea; isopropylguanylurea; butylguanylurea; benzylguanylurea; phenylguanylurea; tolylguanybrea; naphthylguanylurea; cyclohexylguanylurea; norbornylguanylurea; adamantylguanylurea; dimethylguanylurea; diethylguanylurea; diisopropylguanylurea; dibutylguanylurea; dibenzylguanylurea; diphenylguanylurea; ditolylguanylurea; dinaphthylguanylurea; dicyclohexylguanylurea; dinorbornylguanylurea; diadamantylguanylurea; ethylenebis(guanylurea); propylenebis(guanylurea); phenylenebis(guanylurea); piperazinebis(guanylurea); oxalylbis(guanylurea); malonylbis(guanylurea); succinylbis(guanylurea); phthalylbis(guanylurea); 2-ureidothiazole; 2-ureidooxazole; 2-ureidoimidazole; 3-ureidopyrazole; 3-ureido-1,2,4-triazole; and 5-ureidotetrazole.
[0290] N—O Valence Stabilizer #3: Examples of amidinoamides, guanidinoamides, bis(amidinoamides), bis(guanidinoamides), poly(amidinoamides), and poly(guanidinoamides) (including both N-amidinoamides and 2-amidinoacetamides) (N—O Bidentates, N—O Tridentates, and N—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: amidinoacetamide (1-acetylguanidine); guanidinoacetamide; amidinopropanamide; amidinobutanamide; amidinobenzamide; amidinotoluamide; amidinocyclohexamide; N-methylamidinoacetamide; N-ethylamidinopropanamide; N-propylamidinobutanamide; N-phenylamidinobenzamide; N-tolylamidinotoluamide; N-cyclohexylamidinocyclohexamide; bis(amidinooxamide); bis(amidinomalonamide); bis(amidinosuccinamide); bis(amidinophthalamide); 2-amidinoacetamide (malonamamidine); N-methyl-2-amidinoacetamide; N-ethyl-2-amidinoacetamide; N-phenyl-2-amidinoacetamide; N-benzyl-2-amidinoacetamide; N-cyclohexyl-2-amidinoacetamide; N,N′-dimethyl-2-amidinoacetamide; N,N′-diethyl-2-amidinoacetamide; N,N′-diphenyl-2-amidinoacetamide; N,N′-dibenzyl-2-amidinoacetamide; N,N′-dicyclohexyl-2-amidinoacetamide; 2-N-acylaminothiazole; 2-N-acylaminooxazole; 2-N-acylaminoimidazole; 3-N-acylaminopyrazole; 3-N-acylamino-1,2,4-triazole; and 5-N-acyl aminotetrazole.
[0291] N—O Valence Stabilizer #4: Examples of imidoylamides, bis(imidoylamides), and poly(imidoylamides) (N—O Bidentates, N—O Tridentates, and N—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: acetimidoylacetamide; acetimidoylpropanamide; acetimidoylbutanamide; acetimidoylbenzamide; acetimidolytoluamide; acetimidoylcyclohexamide; propimidoylpropanamide; butimidoylbutanamide; benzimidoylbenzamide; ethylenebis(acetimidoylacetamide); propylenebis(acetimidoylacetamide); and phenylenebis(acetimidoylacetamide).
[0292] N—O Valence Stabilizer #5: Examples of O-amidinocarbamates, bis(O-amidinocarbamates), and poly(O-amidinocarbamates) (N—O Bidentates and N—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: O-amidinocarbamate; N-methyl-O-amidinocarbamate; N-ethyl-O-amidinocarbamate; N-isopropyl-O-amidinocarbamate; N-butyl-O-amidinocarbamate; N-benzyl-O-amidinocarbamate; N-phenyl-O-amidinocarbamate; N-tolyl-O-amidinocarbamate; N-naphthyl-O-amidinocarbamate; N-cyclohexyl-O-amidinocarbamate; N-norbornyl-O-amidinocarbamate; N-adamantyl-O-amidinocarbamate; N,N′-dimethyl-O-amidinocarbamate; N,N′-diethyl-O-amidinocarbamate; N,N′-diisopropyl-O-amidinocarbamate; N,N′-dibutyl-O-amidinocarbamate; N,N′-dibenzyl-O-amidinocarbamate; N,N′-diphenyl-O-amidinocarbamate; N,N′-ditolyl-O-amidinocarbamate; N,N′-dinaphthyl-O-amidinocarbamate; N,N′-dicyclohexyl-O-amidinocarbamate; N,N′-dinorbornyl-O-amidinocarbamate; N,N′-diadamantyl-O-amidinocarbamate; ethylenebis(O-amidinocarbamate); propylenebis(O-amidinocarbamate); phenylenebis(O-amidinocarbamate); piperazinebis(O-amidinocarbamate); oxalylbis(O-amidinocarbamate); malonylbis(O-amidinocarbamate); succinylbis(O-amidinocarbamate); phthalylbis(O-amidinocarbamate); 2-O-carbamatothiazole; 2-O-carbamatooxazole; 2-O-carbamatoimidazole; 3-O-carbamatopyrazole; 3-O-carbamato-1,2,4-triazole; and 5-carbamatotetrazole.
[0293] N—O Valence Stabilizer #6; Examples of S-amidinothiocarbamates, bis(S-amidinothiocarbamates), and poly(S-amidinothiocarbamates) (N-O Bidentates and N—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: S-amidinothiocarbamate; N-methyl-S-amidinothiocarbamate; N-ethyl-S-amidinothiocarbamate; N-isopropyl-S-amidinothiocarbamate; N-butyl-S-amidinothiocarbamate; N-benzyl-S-amidinothiocarbamate; N-phenyl-S-amidinothiocarbamate; N-tolyl-S-amidinothiocarbamate; N-naphthyl-S-amidinothiocarbamate; N-cyclohexyl-S-amidinothiocarbamate; N-norbornyl-S-amidinothiocarbamate; N-adamantyl-S-amidinothiocarbamate; N,N′-dimethyl-S-amidinothiocarbamate; N,N′-diethyl-S-amidinothiocarbamate; N,N′-diisopropyl-S-amidinothiocarbamate; N,N′-dibutyl-S-amidinothiocarbamate; N,N′-dibenzyl-S-amidinothiocarbamate; N,N′-diphenyl-S-amidinothiocarbamate; N,N′-ditolyl-S-amidinothiocarbamate; N,N′-dinaphthyl-S-amidinothiocarbamate; N,N′-dicyclohexyl-S-amidinothiocarbamate; N,N′-dinorbornyl-S-amidinothiocarbamate; N,N′-diadamantyl-S-amidinothiocarbamate; ethylenebis(S-amidinothiocarbamate); propylenebis(S-amidinothiocarbamate); phenylenebis(S-amidinothiocarbamate); piperazinebis(S-amidinothiocarbamate); oxalylbis(S-amidinothiocarbamate); malonylbis(S-amidinothiocarbamate); succinylbis(S-amidinothiocarbamate); phthalylbis(S-amidinothiocarbamate); 2-O-monothiocarbamatothiazole; 2-O-monothiocarbamatooxazole; 2-O-monothiocarbamatoimidazole; 3-O-monothiocarbamatopyrazole; 3-O-monothiocarbamato-1,2,4-triazole; and 5-O-monothiocarbamatotetrazole.
[0294] N—O Valence Stabilizer #7: Examples of diimidosulfuric acid, bis(diimidosulfuric acid), and derivatives thereof (N—O Bidentates and N—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diimidosulfuric acid; O-phenyldiimidosulfuric acid; O-benzyldiimidosulfuric acid, O-cyclohexyldiimidosulfuric acid, O-norbornyldiimidosulfuric acid, O,O′-diphenyldiimidosulfuric acid; O,O′-dibenzyldiimidosulfuric acid, O,O′-dicyclohexyldiimidosulfuric acid, and O,O′-dinorbornyldiimidosulfuric acid.
[0295] N—O Valence Stabilizer #8: Examples of phosphorimidic acid, bis(phosphorimidic acid); and poly(phosphorimidic acid), and derivatives thereof (N—O Bidentates, N—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: phosphorimidic acid; O-phenylphosphorimidic acid; O-benzylphosphorimidic acid; O-cyclohexylphosphorimidic acid; O-norbornylphosphorimidic acid; O,O′-diphenylphosphorimidic acid; O,O′-dibenzylphosphorimidic acid; O,O′-dicyclohexylphosphorimidic acid; and O,O′-dinorbornylphosphorimidic acid.
[0296] N—O Valence Stabilizer #9: Examples of phosphoric triamides, bis(phosphoric triamides), and poly(phosphoric triamides) (N—O Bidentates and N—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: phosphoric triamide; phosphoramidic dihydrazide; N-phenylphosphoric triamide, N-benzylphosphoric triamide; N-cyclohexylphosphoric triamide; N-norbornylphosphoric triamide; N,N′-diphenylphosphoric triamide, N,N′-dibenzylphosphoric triamide; N,N′-dicyclohexylphosphoric triamide; and N,N′-dinorbornylphosphoric triamide.
[0297] N—O Valence Stabilizer #10: Examples of phosphoramidic acid, phosphorodiamidic acid, bis(phosphoramidic acid), bis(phosphorodiamidic acid), poly(phosphoramidic acid), poly(phosphorodiamidic acid), and derivatives thereof (N—O Bidentates and N—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: phosphoramidic acid, phosphorodiamidic acid, phosphoramidohydrazidic acid; phosphorohydrazidic acid; phosphorodihydrazidic acid; O-phenylphosphoramidic acid; O-benzylphosphoramidic acid; O-cyclohexylphosphoramidic acid; O-norbornylphosphoramidic acid; O,O′-diphenylphosphoramidic acid; O,O′-dibenzylphosphoramidic acid; O,O′-dicyclohexylphosphoramidic acid; and O,O′-dinorbornylphosphoramidic acid.
[0298] N—O Valence Stabilizer #11: Examples of N-acyl 7-aminobenzylidenimines (N—O Bidentates or N—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N-acetyl 7-methylaminobenzylidenimine; N-acetyl 7-phenylaminobenzylidenimine; N-benzoyl 7-methylaminobenzylidenimine; and N-benzoyl 7-phenylaminobenzylidenimine.
[0299] N—O Valence Stabilizer #12: Examples of oximes, dioximes, and poly(oximes) (N—O Bidentates, N—O Tridentates, and N—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: acetaldoxime (Hado); acetoxime (acetone oxime)(Hato); butanone oxime; pentanone oxime; hexanone oxime; pinacolone oxime; heptanone oxime; octanone oxime; cyclopentanone oxime; cyclohexanone oxime; cycloheptanone oxime; cyclooctanone oxime; cyclopentanedione dioxime; cyclohexanedione dioxime; cycloheptanedione dioxime; cyclooctanedione dioxime; isatin dioxime; benzaldehyde oxime; naphthaldehyde oxime; norbornanone oxime; camphor oxime; dimethylglyoxime (H2DMG); diethylglyoxime; diisopropylglyoxime; ditertbutylglyoxime; dicyanoglyoxime; dicyanamidoglyoxime; diphenylglyoxime (Hdfg); dibenzylglyoxime; dicyclohexylglyoxime; dinorbornylglyoxime; camphorquinone dioxime (Hcqd); nopinoquinone dioxime (Hnqd); butyraldoxime; propionaldoxime; furildioxime; and thienyldioxime.
[0300] N—O Valence Stabilizer #13: Examples of carbonyl oximes, bis(carbonyl oximes), and poly(carbonyl oximes) (N—O Bidentates, N—O Tridentates, and N—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diacetyl monoxime (2,3-butanedione monoxime); benzil monoxime (1,2-diphenylethanedione monoxime); 1,2-dicyclohexylethanedione monoxime; 1,2-(trifluoromethyl)ethanedione monoxime; 1,2-dinorbornylethanedione monoxime; cyclopentanedione monoxime; cyclohexanedione monoxime; cycloheptanedione monoxime; cyclooctanedione monoxime; camphorquinone oxime; 3-hydroxyiminopentane-2,4-dione; and 4-isonitrosopyralozone.
[0301] N—O Valence Stabilizer #14: Examples of imine oximes, bis(imine oximes), and poly(imine oximes) (including 2-nitrogen heterocyclic oximes) (N—O Bidentates, N—O Tridentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 3-(methylimino)butan-2-one oxime; 4-(methylimino)hexan-3-one oxime; 1,2-dipbenyl-2-(methylimino)ethan-1-one oxime; 1,2-diphenyl-2-(phenylimino)ethan-1-one oxime; 1,2-dicyclohexyl-2-(methylimino)ethan-1-one oxime; 1,2-dicyclohexyl-2-(cyclohexylimino)ethan-1-one oxime; 1,2-dinorbornyl-2-(methylimino)ethan-1-one oxime; N,N′-methylenebis-(3-iminobutan-2-one oxime); N,N′-methylenebis-(4-iminohexan-3-one oxime); N,N′-methylenebis-(1,2-diphenyl-2-iminoethan-1-one oxime); N,N′-methylenebis-(1,2-dicyclohexyl-2-iminoethan-1-one oxime); N,N′-methylenebis-(1,2-dinorbornyl-2-iminoethan-1-one oxime); N,N′-ethylenebis-(3-iminobutan-2-one oxime); N,N′-ethylenebis-(4-iminohexan-3-one oxime); N,N′-ethylenebis-(1,2-diphenyl-2-iminoethan-1-one oxime); N,N′-ethylenebis-(1,2-dicyclohexyl-2-iminoethan-1-one oxime); N,N′-ethylenebis-(1,2-dinorbornyl-2-iminoethan-1-one oxime); N,N′-propylenebis-(3-iminobutan-2-one oxime); N,N′-propylenebis-(4-iminohexan-3-one oxime); N,N′-propylenebis-(1,2-diphenyl-2-iminoethan-1-one oxime); N,N′-propylenebis-(1,2-dicyclohexyl-2-iminoethan-1-one oxime); N,N′-propylenebis-(1,2-dinorbornyl-2-iminoethan-1-one oxime); diacetylazine oxime (Hazio); 2-pyridinaldoxime (Hpao); methyl 2-pyridyl ketone oxime; ethyl 2-pyridyl ketoxime; phenyl 2-pyridyl ketone oxime (Hppk); benzyl 2-pyridyl ketoxime; di(2-pyridyl) ketone oxime; methyl 2-pyrrolyl ketone oxime; ethyl 2-pyrrolyl ketone oxime; phenyl 2-pyrrolyl ketone oxime; di(2-pyrrolyl) ketone oxime; and tris(2-aldoximo-6-pyridyl)phosphine.
[0302] N—O Valence Stabilizer #15: Examples of hydroxy oximes, bis(hydroxy oximes), and poly(hydroxy oximes) (including 2-oxygen heterocyclic oximes) (N—O Bidentates, N—O Tridentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 3-hydroxybutan-2-one oxime; 4-hydroxyhexan-3-one oxime; benzoin oxime (bo)(1,2-diphenyl-2-hydroxyethanone oxime); 1,2-di(trifluoromethyl)-2-hydroxyethanone oxime; 1,2-dicyclohexyl-2-hydroxyethanone oxime; 1,2-dinorbornyl-2-hydroxyethanone oxime; salicylaldoxime (so)(saldox); 2-hydroxy-1-naphthaldehyde oxime; 2-furanaldoxime; furildioxime; methyl 2-furanyl ketone oxime; ethyl 2-furanyl ketoxime; phenyl 2-furanyl ketone oxime; benzyl 2-furanyl ketoxime; di(2-furanyl) ketone oxime; and 2,5-(oximinomethyl)phenol.
[0303] N—O Valence Stabilizer #16: Examples of amino oximes, bis(amino oximes), and poly(amino oximes) (N—O Bidentates, N—O Tridentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 3-(methylamino)butan-2-one oxime (HMeabo); 4-(methylamino)hexan-3-one oxime (HEtabo); 1,2-diphenyl-2-(methylamino)ethanone oxime (HPhabo); 1,2-diphenyl-2-(phenylamino)ethanone oxime; 1,2-dicyclohexyl-2-(methylamino)ethanone oxime (HcyHxabo); 1,2-dicyclohexyl-2-(cyclohexylamino)ethanone oxime; 1,2-di(trifluoromethyl)-2-(methylamino)ethanone oxime; 1,2-dinorbornyl-2-(methylamino)ethanone oxime (HNorbabo); N,N′-ethylenebis-(3-aminobutan-2-one oxime)(Haboen); N,N′-ethylenebis-(4-aminohexan-3-one oxime); N,N′-ethylenebis-(1,2-diphenyl-2-aminoethanone oxime); N,N′-ethylenebis-(1,2-dicyclohexyl-2-aminoethanone oxime); N,N′-ethylenebis-(1,2-di(trifluoromethyl)-2-aminoethanone oxime); N,N′-ethylenebis-(1,2-dinorbornyl-2-aminoethanone oxime); N,N′-propylenebis-(3-aminobutan-2-one oxime)(Habopn); N,N′-propylenebis-(4-aminohexan-3-one oxime); N,N′-propylenebis-(1,2-diphenyl-2-aminoethanone oxime); N,N′-propylenebis-(1,2-dicyclohexyl-2-aminoethanone oxime); N,N′-propylenebis-(1,2-di(trifluoromethyl)-2-aminoethanone oxime); N,N′-propylenebis-(1,2-dinorbornyl-2-aminoethanone oxime); 2,2′-iminobis(acetamidoxime); 1-diethylamino-3-butanoxime; and di-2-pyridyl ketone oxime.
[0304] N—O Valence Stabilizer #17: Examples of amido oximes, bis(amido oximes), and poly(amido oximes) (N—O Bidentates, N—O Tridentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: formamide oxime; acetamide oxime; propanamide oxime; butanamide oxime; benzamide oxime (Hbamox); naphthamide oxime; diformamide dioxime; salicylamide oxime; and 4-imidazolamide oxime.
[0305] N—O Valence Stabilizer #18: Examples of azo oximes, bis(azo oximes), and poly(azo oximes) (N—O Bidentates, N—O Tridentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: acetaldehyde phenylhydrazone oxime; propionaldehyde phenylhydrazone oxime; and benzaldehyde phenylhydrazone oxime. Also includes hydrazone oximes.
[0306] N—O Valence Stabilizer #19: Examples of 2-nitrosophenols (o-quinone monoximes) (N—O Bidentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-nitrosophenol; 1-nitroso-2-naphthol (Honn); 2-nitroso-1-naphthol (Htnn); 3-nitrosopyrocatechol; 3,6-dinitrosopyrocatechol; 2-nitrosoresorcinol; 2,4-dinitrosoresorcinol; 2,4,6-trinitrosoresorcinol; 2-nitrosohydroquinone; 2,6-dinitrosohydroquinone; 2,3,5,6-tetranitrosohydroquinone; 4-nitrosopyrogallol; 4,6-dinitrosopyrogallol; 2-nitrosophloroglucinol; 2,4,6-trinitrosophloroglucinol; 7-nitroso-6-hydroxyindazole; Pigment Green 12 (C.I. 10020); Naphthol Green; and nitroso-R-salt.
[0307] N—O Valence Stabilizer #20: Examples of 2-nitrophenols (N—O Bidentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-nitrophenol; 2,3-dinitrophenol; 2,4-dinitrophenol; 2,5-dinitrophenol; 2,6-dinitrophenol; 2,4,6-trinitrophenol (picric acid); 2-amino-4,6-dinitrophenol (picramic acid); 1-nitro-2-naphthol; 2-nitro-1-naphthol; 3-nitropyrocatechol; 3,6-dinitropyrocatechol; 2-nitroresorcinol; 2,4-dinitroresorcinol; 2,4,6-trinitroresorcinol (styphnic acid); 2-nitrohydroquinone; 2,6-dinitrohydroquinone; 2,3,5,6-tetranitrohydroquinone; 4-nitropyrogallol; 4,6-dinitropyrogallol; 2-nitrophloroglucinol; 2,4,6-trinitrophloroglucinol; dinitrocresol; 7-nitro-6-hydroxyindazole; Dinoseb; Eosin; Naphthol Yellow; and Martius Yellow.
[0308] N—O Valence Stabilizer #21: Examples of hydroxamates (hydroxylamines), bis(hydroxamates), and poly(hydroxamates) (N—O Bidentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: acetohydroxamic acid; propianohydroxamic acid; butyrohydroxamic acid; crotonohydroxamic acid; sorbohydroxamic acid; benzohydroxamic acid (BH2); toluichydroxamic acid; salicylhydroxamic acid (SH2); phenylacetohydroxamic acid (PhH2); anthranilhydroxamic acid (AnH2); nicotinehydroxamic acid (NiCH2); picolinehydroxamic acid; cyclohexanehydroxamic acid (CH2); quinoline 8-hydroxamic acid (QH2); cinnamylhydroxamic acid (CnH2); oxaldihydroxamic acid (OxalH2); succinylbis-N-phenylhydroxamic acid (SuH2); adipylbis-N-phenylhydroxamic acid (AdH2); glyoxalhydroxamic acid (GH2); 2-tbiophenecarbohydroxamic acid; thenoylhydroxamic acid; N-phenylbenzohydroxamic acid; N-tolylbenzohydroxamic acid; N-phenylacetohydroxamic acid; N-phenyl-2-thenoylhydroxamic acid; N-tolyl-2-thenoylhydroxamic acid; and polyhydroxamic acids.
[0309] N—O Valence Stabilizer #22: Examples of N-nitrosohydroxylamines, bis(N-nitrosohydroxylamines), and poly(N-nitrosohydroxylamines) (N—O Bidentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N-nitrosophenylhydroxylamine (cupferron); N-nitrosonaphthylhydroxylamine (neocupferron); N-nitrosoanthracylhydroxylamine; N-nitroso(2-pyridyl)hydroxylamine; and N-nitroso(2-thiophenyl)hydroxylamine.
[0310] N—O Valence Stabilizer #23: Examples of amino acids, ortho-aminocarboxylic acids, peptides, polypeptides, and proteins [N—O Bidentates, N—O Tridentates, and N—O Tetradentates; possibly S—O dentates for sulfur-contg. examples such as penicillamine and cystine] that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: alanine (Ala); arginine (Arg); asparagine (Asn); aspartic acid (Asp); cysteine (Cys); cystine (Cys or Cys.Cys); dihydroxyphenylalanine (Dopa); glutamic acid (Glu); glutamine (Gin); glycine (Gly); histidine (His); isoleucine (Ile); leucine (Leu); lysine (Lys); methionine (Met); penicillamine (Pen); phenylalanine (Phe); tolylalanine (tala); proline (Pro); sarcosine; serine (Ser); threonine (Thr); tryptophan (Trp); tyrosine (Tyr); and valine (Val) as amino acid examples; 2-pyridinecarboxylic acid (picolinic acid), 2-pyrazinecarboxylic acid, 2,3-dicarboxypyrazine, and anthranilic acid as ortho-aminocarboxylic acid examples; Gly-GluO; Hgly-Gly; Gly-MetO; Met-GlyO; Gly-TyrO; Ala-H is O; Gly-His-GlyO; Gly-Gly-His; Gly-Leu-TyrO; penta-GlyO; His-His; triaminoisobutyrate; tetra-GlyO; Pro-Gly; and Gly-Met as peptide examples; and azurin, carbonic anhydrase C; carboxypeptidase; concanavalin A; cytochrome b; cytochrome c; erythrocruorin; ferredoxin; haemerythrin; haemoglobin; myoglobin; parvalbumin; albumin; plastocyanin; rubredoxin; superoxide dismutase; thermolysin; and trysin as protein examples; N-acylamino acids; aminocaproic acid; and 3,5-diiodotyrosine.
[0311] N—O Valence Stabilizer #24: Examples of amides, bis(amides), and poly(amides), including lactams (N—O bidentates, N—O tridentates, and N—O tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: acetamide; propionamide; butanamide; benzamide (benzoylamide)(1-phenylformamide); 1-naphthylformamide; toluamide; 1-cyclohexylformamide); 1-norbornylformamide; 1-adamantylform amide; N,N-dimethylformamide (DMF)(DMFA); N,N-dimethylacetamide (DMAC); N,N-dimethylbenzamide; N,N-diethylformamide; N,N-diethylacetamide; decanamide; dodecanamide; tetradecanamide; hexadecanamide; octadecanamide; lactobionic acid amide; (hydroxyalkylthio)succinamides; (mercaptoalkoxy)succinamides; polycaproamides; glycinamide; aminoalkylanilides; amidopolyamines (apa); bis(1-phenylethylamide); oxalic semiamide; malonic semiamide; succinic semiamide; bis(1,1′-benzotriazolyl)dicarboxamide; nicotinamide; acetanilide (N-phenylacetamide); formanilide (N-phenylformamide); benzanilide (N-phenylbenzamide); N-methylformanilide; acetanilide; nicotinanilide; 4′-hydroxyacetanilide (acetaminophen); 2-pyrrolidone; methyl-2-pyrrolidone (NMP); 2-piperidone (valerolactam); caprolactam; polymethylenepolyamine dipropionamide; polyacrylamides; polypyrrolidones [including polyvinylpyrrolidone (povidone)(PVP)]; pyrazolidinones; pyrazolones; diazepinones; N-alkylazaalkene lactams; and N-(2-hydroxyalkyl)azaalkene lactams.
[0312] N—O Valence Stabilizer #25: Examples of semicarbazones, bis(semicarbazones), and poly(semicarbazones) (N—O Bidentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: acetaldehyde semicarbazone; acetone semicarbazone; pinacolone semicarbazone; benzaldehyde semicarbazone; naphthaldehyde semicarbazone; norbornanone semicarbazone; camphor semicarbazone; nopinone semicarbazone; 2-pyridinaldehyde semicarbazone; salicylaldehyde semicarbazone; quinolinaldehyde semicarbazone; isatin disemicarbazone; camphorquinone disemicarbazone; camphorquinone disemicarbazone; picolinaldehyde semicarbazone; dipyridyl glyoxal disemicarbazone; di-2-pyridyl ketone semicarbazone; methyl-2-pyridyl ketone semicarbazone; glyoxal disemicarbazone; acetophenone semicarbazone; biacetyl monoxime semicarbazone; acetamidobenzaldehyde semicarbazone; thymolaldosemicarbazone; thiophene-2-aldehyde semicarbazone; phthalaldehyde disemicarbazone; phthalimide disemicarbazone; furaldehyde semicarbazone; naphthoquinone semicarbazone; phenanthrequinone semicarbazone; cyclohexanedione disemicarbazone; ionone semicarbazone; bissemicarbazone of diethyl-3,4-dioxadioate; and lawsone semicarbazone.
[0313] N—O Valence Stabilizer #26: Examples of acyl hydrazones, bis(acyl hydrazones), and poly(acyl hydrazones) (N—O Bidentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: acetaldehyde N-formylhydrazone; acetaldehyde N-benzoylhydrazone; acetone N-formylhydrazone; acetone N-benzoylhydrazone; pinacolone N-formylhydrazone; pinacolone N-benzoylhydrazone; benzaldehyde N-formylhydrazone; benzaldehyde N-benzoylhydrazone; naphthaldehyde N-formylhydrazone; naphthaldehyde N-benzoylhydrazone; norbornanone N-formylhydrazone; norbornanone N-benzoylhydrazone; camphor N-formylhydrazone; camphor N-benzoylhydrazone; nopinone N-formylhydrazone; nopinone N-benzoylhydrazone; 2-pyridinaldehyde N-formylhydrazone; 2-pyridinalde hyde N-benzoylhydrazone; salicylaldehyde N-formylhydrazone; salicylaldehyde N-benzoylhydrazone; quinolinaldehyde N-formylhydrazone; quinolinaldehyde N-benzoylhydrazone; furan-2-aldehyde N-formylhydrazone; furan-2-aldehyde N-benzoylhydrazone; naphthoquinone N-formylhydrazone; naphthoquinone N-benzoylhydrazone; ionone N-formylhydrazone; ionone N-benzoylhydrazone; lawsone N-formylhydrazone; and lawsone N-benzoylhydrazone.
[0314] N—O Valence Stabilizer #27: Examples of carbazones (diazenecarboxylic hydrazides), bis(carbazones), and poly(carbazones) (N—O Bidentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diphenylcarbazone; 2-phenylcarbazone; dinaphthylcarbazone; and 2-naphthylcarbazone.
[0315] N—O Valence Stabilizer #28: Examples of azo compounds with hydroxyl or carboxy or carbonyl substitution at the ortho- (for aryl) or alpha- or beta- (for alkyl) positions, Bis[o-(HO—) or alpha- or beta-(HO—)azo compounds], or Poly[o-(HO—) or alpha- or beta-(HO—)azo compounds) (N—O Bidentates, N—O Tridentates, N—O Tetradentates, or N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-hydroxyazobenzene [1-(phenylazo)-2-phenol]; 2,2′-dihydroxyazobenzene (o,o′-dihydroxyazobenzene); (2-furan)azobenzene; Direct Blue 2B; 1-(4-nitrophenylazo)-2-naphthol; 1-(2-hydroxyphenylazo)-2-naphthol; 1-(2-methoxyphenyl azo)-2-naphthol; pyridineazo-2-naphthol (PAN); pyridineazoresorcinol (PAR); 1-phenyl-4-(2-hydroxyphenylazo)-5-pyrazolone; 1-phenyl-4-(2-methoxyphenylazo)-5-pyrazolone; o-hydroxy-o′-(beta-aminoethylamino)azobenzene; 2-hydroxy-2′-methoxymethyleneoxyazobenzene; methyl red; turquoise blue (reactive blue); sunset yellow; amaranth; tartrazine; Eriochrome Black T; tropeolins; Allura Red; amaranth; Acid Alizarin Violet N; Acid Blue 29; Acid Orange 8, 63, and 74; Acid Red 1, 4, 8, 37, 88, 97, 114, 151, and 183; Acid Violet 7; Acid Yellow 25, 29, 34, 42, 76, and 99; Brilliant Black BN; Brilliant Crocein; Bordeaux R; Calcion; Chicago Sky Blue; Chromotrope; Cibacron Brilliant Red; Cibacron Brilliant Yellow; Crocein Orange; Crystal Scarlet; Calmagite; Direct Blue 71; Direct Red 23, 80, and 81; Direct Violet 51; Direct Yellow 8 and 27; Fast Black; Flavazin; Mordant Blue 9; Mordant Brown 1 and 33; Napthol Blue Black; New Coccine; Nitrazine Yellow; Nitrosulfonazo III; Orange II; Orange G, OT, and B; Ponceau 3R and SX; Polar Yellow; 2-oxazolylazobenzene; and 2-benzoxazolylazobenzene.
[0316] N—O Valence Stabilizer #29: Examples of diazeneformamides, diazeneacetamides, bis(diazenefonmamides), bis(diazeneacetamides), poly(diazeneformamides), and poly(diazeneacetamides) (N—O Bidentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diazeneformamide, diazeneacetamide, phenyldiazeneformamide, diphenyldiazeneformamide, phenyldiazeneacetamide, and diphenyldiazeneacetamide.
[0317] N—O Valence Stabilizer #30: Examples of diazeneformic acids, diazeneacetic acids, bis(diazeneformic acids), bis(diazeneacetic acids), poly(diazeneformic acids), poly(diazeneacetic acids) and derivatives thereof (N—O Bidentates, N—O Tetradentates, N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diazeneformic acid, diazeneacetic acid, phenyldiazeneformic acid, diphenyldiazeneformic acid, phenyldiazeneacetic acid, and diphenyldiazeneacetic acid.
[0318] N—O Valence Stabilizer #31: Examples of diazenefonmaldehydes, diazeneacetaldehydes, bis(diazeneformaldehydes), bis(diazeneacetaldehydes), poly(diazenefonmaldehydes), and poly(diazeneacctaldehydes) (N—O Bidentates, N—O Tetradentates and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diazenefonmaldehyde, diazeneacetaldehyde, phenyldiazeneformaldehyde, diphenyldiazeneformaldehyde, phenyldiazeneacetaldehyde, and diphenyldiazeneacetaldehyde.
[0319] N—O Valence Stabilizer #32: Examples of diazenediformamides, diazenediacetamides, bis(diazenediformamides), bis(diazenediacetamides), poly(diazenedifonmamides), and poly(diazenediacetamides) (N—O Tridentates and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diazenedifonmamide, diazenediacetamide, diphenydiazenediformamide, tetraphenyldiazenediformamide, diphenyldiazenediacetamide, and tetraphenyldiazenediacetamide.
[0320] N—O Valence Stabilizer #33: Examples of diazenediformic acids, diazenediacetic acids, bis(diazenediformic acids), bis(diazenediacetic acids), poly(diazenediformic acids), poly(diazenediacetic acids) and derivatives thereof (N—O Tridentates and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diazenediformic acid, diazenediacetic acid, phenyldiazenediformic acid, diphenyldiazenediformic acid, phenyldiazenediacetic acid, and diphenyldiazenediacetic acid.
[0321] N—O Valence Stabilizer #34: Examples of diazenedifonmaldehydes, diazenediacetaldehydes, bis(diazenediformaldehydes), bis(diazenediacetaldehydes), poly(diazenedifonmaldehydes), and poly(diazenediacetaldehydes) (N—O Tridentates and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+ include, but are not limited to: diazenedifonmaldehyde, diazenediacetaldehyde, diphenyldiazenediformaldehyde, and diphenyldiazenediacetaldehyde.
[0322] N—O Valence Stabilizer #35: Examples of ortho-hydroxy (or -carboxy) substituted formazans, bis(o-hydroxy or -carboxy substituted formazans), and poly(o-hydroxy or carboxy substituted formazans) (N—O Bidentates, N—O Tridentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 1-(2-hydroxyphenyl)-3,5-diphenylformazan; 1-(2-methoxyphenyl)-3,5-diphenylformazan; 1,5-bis(2-hydroxyphenyl)-3-phenylformazan; and 5-bis(2-methoxyphenyl)-3-phenylformazan.
[0323] N—O Valence Stabilizer #36: Examples of ortho-hydroxy (or -carboxy) substituted azines (including ketazines), bis(o-hydroxy or carboxy substituted azines), and poly(o-hydroxy or carboxy substituted azines) (N—O Bidentates, N—O Tridentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-hydroxy-1-benzalazine; 2-hydroxy-1-naphthalazine; and 2-hydroxy-1-cyclohexanonazine.
[0324] N—O Valence Stabilizer #37: Examples of Schiff Bases with one Imine (C═N) Group and with ortho- or alpha-or beta-hydroxy or carboxy or carbonyl substitution (N—O Bidentates, N—O Tridentates, N—O Tetradentates, N—O Pentadentates, or N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N-(Salicylaldehydo)isopropylamine; N-(2-Furfuralo)isopropylamine; N-(2-Acetylfurano)isopropylamine; N-(2-H ydroxyacetophenono)isopropylamine; N-(Pyridoxalo)isopropylamine; N-(Salicylaldehydo)cyclohexylamine; N-(2-Furfuralo)cyclohexylamine; N-(2-Acetyl furano)cyclohexylamine; N-(2-Hydroxyacetophenono)cyclohexylamine; N-(Pyridoxalo)cyclohexylamine; N-(Salicylaldehydo)aniline; N-(2-Furfuralo)aniline (Stenhauz salt); N-(2-Acetylfurano)aniline; N-(2-Hydroxyacetophenono)aniline; N-(Pyridoxalo)aniline; N-(Salicylaldehydo)aminonorbornane; N-(2-Furfuralo)aminonorbornane; N-(2-Acetylfurano)aminonorbornane; N-(2-Hydroxyacetophenono)aminonorbornane; N-(Pyridoxalo)aminonorbornane; (Salicylaldehydo)anisidine; 2-salicylideneiminobenzothiazole; (Salicylaldehydo)sulfamethazine; and N′-histidine-3-methoxysalicylidenimine (V-his); N-(o-carboxybenzaldehydo)-2-aminophenol; N-(salicylaldehydo)isatin; N-(2-furfuralo)isatin; N-(2-acetylfurano)isatin; N-(pyridoxalo)isatin; N-(2-hydroxyacetophenono)isatin; hydrofuramide; 2-furancarboxaldehyde phenylhydrazone; 2-furancarboxaldehyde 2-pyridyl hydrazone; salicylaldehyde phenylhydrazone; and salicylaldehyde 2-pyridyl hydrazone. Also includes hydrazones with ortho-O substitution.
[0325] N—O Valence Stabilizer #38: Examples of Schiff Bases with two Imine (C═N) Groups and with ortho- or alpha- or beta-hydroxy or carboxy or carbonyl substitution (N—O Tridentates, N—O Tetradentates, N—O Pentadentates, or N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N,N′-(2,5-Furandicarboxaldehydo)diisopropylamine; N,N′-(2,5-Furandicarboxaldehydo)dicyclohexylamine; N,N′-(2,5-Furandicarboxaldehydo)dianiline; N,N′-(2,5-Furandicarboxaldehydo)di-aminonorbornane; N,N′-(o-Hydroxyphthalicdialdehydo)diisopropylamine; N,N′-(o-Hydroxyphthalicdialdehydo)dicyclohexylamine; N,N′-(o-Hydroxyphthalicdialdehydo)dianiline; N,N′-(o-Hydroxyphthalicdialdehydo)di-aminonorbornane; N,N′-(o-Hydroxyformylcamphoro)diisopropylamine; N,N′-(o-Hydroxyformylcamphoro)dicyclohexylamine; N,N′-(o-Hydroxyformylcamphoro)dianiline; N,N′-(o-Hydroxyformylcamphoro)di-aminonorbornane; N,N′-(o-Hydroxydiacetylbenzeno)diisopropylamine; N,N′-(o-Hydroxydiacetylbenzeno)dicyclohexylamine; N,N′-(o-Hydroxydiacetylbenzeno)dianiline; N,N′-(o-Hydroxydiacetylbenzeno)di-aminonorbornane; N,N′-(3,6-Dihydroxy-1,2-cyclohexanono)diisopropylamine; N,N′-(3,6-Dihydroxy-1,2-cyclohexanono)dicyclohexylamine; N,N′-(3,6-Dihydroxy-1,2-cyclohexanono)dianiline; N,N′-(3,6-Dihydroxy-1,2-cyclohexanono)di-aminonorbornane; N,N′-(2,5-Diacetyl furano)diisopropyl amine; N,N′-(2,5-Diacetylfurano)dicyclohexylamine; N,N′-(2,5-Diacetylfurano)dianiline; N,N′-(2,5-Diacetylfurano)di-aminonorbornane; N,N′-(Salicylaldehydo)ethylenediamine; N,N′-(o-Hydroxynaphthaldehydo)ethylenediamine; N,N′-(o-Hydroxyacetophenono)ethylenediamine; N,N′-(Salicylaldehydo)trimethylenediamine; N,N′-(o-Hydroxynaphthaldehydo)trimethylenediamine; N,N′-(o-Hydroxyacetophenono)trimethylenediamine; N,N′-(Salicylaldehydo)cyclohexane-1,2-diamine; N,N′-(o-Hydroxynapbthaldehydo)cyclohexane-1,2-diamine; N,N′-(o-Hydroxyacetophenono)cyclohexane-1,2-diamine; N,N′-(Salicylaldehydo) 1,2-diaminobenzene; N,N′-(o-Hydroxynaphthaldehydo)-1,2-diaminobenzene; N,N′-(o-Hydroxyacetophenono)-1,2-diaminobenzene; N,N′-bis(salicylaldehydo)-1,12-diaminododecane (Saldn); N,N′-bis(3-methoxysalicylaldehydo)-o-phenyldiamine; N,N′-bis(3,4-difluorobenzaldehydo)-4,4′-benzidine; and N,N′-phenylenebis(3-methoxysalicylidenimine) (V-ph-V). Also includes hydrazones with ortho-O substitution.
[0326] N—O Valence Stabilizer #39: Examples of Schiff Bases with three Imine (C═N) Groups and with ortho- or alpha- or beta-hydroxy or carboxy or carbonyl substitution (N—O Tetradentates, N—O Pentadentates, or N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N,N′,N″-(Salicylaldehydo)tris(2-aminoethyl)amine; N,N′,N″-(o-Hydroxynaphthaldehydo)tris(2-aminoethyl)amine; and N,N′,N″-(o-Hydroxyacetophenono)tris(2=aminoethyl)amine. Also includes hydrazones with ortho-O substitution.
[0327] N—O Valence Stabilizer #40: Examples of silylaminoalcohols (N—O Bidentates, N—O Tridentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: silatranes.
[0328] N—O Valence Stabilizer #41: Examples of hydroxyalkyl imines (imino alcohols) (N—O Bidentates, N—O Tridentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-hydroxycyclohexylimine; 3-hydroxy-2-iminonorbornane; 2,2′-diiminodicyclohexyl ether; oxamide; 3-imino-1,5-pentanedialdehyde; iminodiacetic acid; and iminodipropionic acid.
[0329] N—O Valence Stabilizer #42: Examples of hydroxyaryl amines and hydroxyaryl imines (NO Bidentates, N—O Tridentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-aminophenol; 2-aminobenzoic acid (anthranilic acid); 2-aminoanisole; o-phenetidine; o-anisidine; 2-hydroxymethyl)-alpha-aminotoluene; 1-amino-2-naphthol; 2-amino-1-naphthol; 2,2′-di(aminomethyl)diphenylketone; isophoronediamine; tris-2,4,6-dimethylaminomethyl phenol; di(2-amino)phenyl ether; 1,3-di(2-amino)phenyl-2-hydroxypropane; 1,3-di(3-amino)phenyl-2-hydroxypropane; 1,3-di(2-hydroxy)phenyl-2-aminopropane; 1,3-di(3-hydroxy)phenyl-2-aminopropane; 2,2′-dihydroxyiminodibenzyl; 2,2′-iminodibenzoic acid; 2,2′-dihydroxyiminostilbene; poly(o-phenetidine); poly(o-aminophenol); poly(o-anisidine); and 3-(anilino)propionamide.
[0330] N—O Valence Stabilizer #43: Examples of five-membered heterocyclic rings containing one, two, three, or four nitrogen atoms at least one additional oxygen atom binding site not in a ring (N—O Bidentates, N—O Tridentates, N—O Tetradentates, or N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-hydroxypyrrole; 2-(methylhydroxy)methylpyrrole; 2,5-(hydroxymethyl)pyrrole; 2,5-(methylhydroxymethyl)pyrrol; imidazoline-2-one (2-hydroxyimidazole); 2-hydroxythiazoline; 2-hydroxybenzimidazole; 2-hydroxybenzothiazole; 2-hydroxybenzoxazole; 2-hydantoin; di-2-pyridylglyoxal (2,2′-pyridil); bis((1-pyrazolyl)methane)ether; bis(2-(1-pyrazolyl)ethane)ether; bis(benzimidazolylmethane)ether; bis(benzimidazolylethane)ether; tris(imidazolyl)methanol; tris(imidazolylmethane)methanol; N-hydroxymethyl-N,N-(benzimidazolylmethane)amine; N-(2-hydroxyethyl)-N,N-(benzimidazolylmethane)amine; N,N′-di(benzimidazolylmethane)-1,3-diamino-2-hydroxypropane; N,N,N′,N′-tetrakis(benzimidazolylmethane)-1,3-diamino-2-hydroxypropane; bis(N,N-((4-imidazolyl)methane)2-aminoethane)ether; 4-carboxybenzotriazole; antipyrine; 4-aminoantipyrine (aap); hydantoin; aminoalkylhydantoins; 2,5-oxazolidinedione; benzyldibenzoyltriazole (bdbt); 5-hydroxymethylimidazole; dicarboxyalkylbenzotriazoles; bis(hydroxyphenyl)aminotriazoles; pyrrole-2-carboxaldehyde; (oxopyrrolidinylalkyl)triazoles; alkoxybenzotriazoles; aryloxybenzotriazoles; 3-salicylamido-4,5-dihydro-1,2,4-triazole; 5-(alkoxy)benzotriazole; (polyoxyalkylene)oxazolidines; 1-(dialkylaminomethyl)-5-carboxyalkylbenzotriazole; 1-(2-hydroxyethyl)imidazoline; 1-acetoxyimidazole; 1-acetylimidazole; benzotriazolecarboxylic acid; poly(oxyalkylated)pyrazoles; poly(oxyalkylated)thiadiazoles; 1,2,4-triazole-3-carboxylic acid; 5-hydroxypyrazole; 3-phenyl-1,2,4-triazol-5-one (ptr); 1-acetylbenzimidazole; 1-[(acetoxy)ethyl]benzimidazole; creatinine; indole-2-carboxylic acid; pyrrole-2-carboxylic acid; imidazole-2-carboxylic acid; pyrazole-2-carboxylic acid; and 1,1′-oxalyldiimidazole.
[0331] N—O Valence Stabilizer #44: Examples of six-membered heterocyclic rings containing one, two, three, or four nitrogen atoms at least one additional oxygen atom binding site not in a ring (N—O Bidentates, N—O Tridentates, N—O Tetradentates, or N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 4-aminomethyl-3-pyridinemethanol (including pyridoxamine); 2-hydroxypyridine; 2-(methylhydroxy)methylpyridine; 2-(2-(methylhydroxy)ethyl)pyridine; 2,6-(hydroxymethyl)pyridine; 2,6-(methylhydroxymethyl)pyridine; 2-hydroxypyrimidine; 2-dihydroxymethylpyrimidine; 2-hydroxyquinoline; 8-hydroxyquinoline (oxine); 8-methylhydroxyquinoline; 2-hydroxyquinazoline; orotic acid (1,2,3,6-tetrahydro-2,6-dioxo-4-pyrimidinecarboxylic acid) (6-uracilcarboxylic acid); 1-methylpyrimidine-2-one; uracil; 6-hydroxypurine; bis(N,N,N′,N′-tetra(2-(2-pyridyl)ethane)aminomethane)ether; bis(N,N,N′,N′-tetra(2-(2-pyridyl)ethane)aminoetbane)ether; quinazol-4-one; quinazol-2-one; 5-azathymine; 2-hydroxybenzimidazole (2-hbz); guanine; 1,3,5-triazin-6-one; 6-hydroxy-1,3,5-triazine; 4,6-dihydroxy-1,3,5-triazine; triazine carboxylic acids; 2,3-dihydroxypyridine; thiomorpholin-3-one; hydroxytetrahydropyrimidines; 2-piperazinones; 2-piperidinones; dilituric acid; actinoquinol; caffeine; citrazinic acid; picolinic acid; 2-quinolol; 2,6-dimethoxypyridine; quinoxaline-2-carboxylic acid; flucytosine; hypoxanthine; hexamethylolmelamine; hydroorotic acid; isoorotic acid; xantbine; leucopterin; nitroorotic acid; 8-azaguanine; and cyanuric acid.
[0332] N—O Valence Stabilizer #45: Examples of five-membered heterocyclic rings containing one or two oxygen atoms at least one additional nitrogen atom binding site not in a ring (N—O Bidentates, N—O Tridentates, N—O Tetradentates, or N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-aminofuran; 2,5-diaminofuran; 2-aminomethylfuran; 2,5-di(aminomethyl)furan; 2-aminobenzofuran; and 2-amino-1,3-dioxolane.
[0333] N—O Valence Stabilizer #46: Examples of six-membered heterocyclic rings containing one or two oxygen atoms at least one additional nitrogen atom binding site not in a ring (N—O Bidentates, N—O Tridentates, N—O Tetradentates, or N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-aminopyran; 2,6-diaminopyran; 2-aminomethylpyran; 2,6-di(aminomethyl)pyran; and 2-aminobenzopyran.
[0334] N—O Valence Stabilizer #47: Examples of five-membered heterocyclic rings containing one, two, three, or four nitrogen atoms at least one additional oxygen atom binding site in a separate ring (N—O Bidentates, N—O Tridentates, N—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-(2-furan)pyrrole; 2,5-di(2-furan)pyrrole; 2-(2-pyran)pyrrole; 2,5-di(2-pyran)pyrrole; 2,5-di(2-pyrrole)furan; and 2,6-di(2-pyrrole)pyran.
[0335] N—O Valence Stabilizer #48: Examples of six-membered heterocyclic rings containing one, two, three, or four nitrogen atoms at least one additional oxygen atom binding site in a separate ring (N—O Bidentates, N—O Tridentates, N—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-(2-furan)pyridine; 2,6-di(2-furan)pyridine; 2-(2-pyran)pyridine; 2,6-di(2-pyran)pyridine; 2,5-di(2-pyridyl)furan; 2,6-di(2-pyridyl)pyran; and drometrizole.
[0336] N—O Valence Stabilizer #49: Examples of two-, three-, four-, six-, eight-, and ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen (usually amine or imine groups) or oxygen (usually hydroxy, carboxy, or carbonyl groups) and are not contained in component heterocyclic rings (N—O Bidentates, N-O Tridentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: azaoxacyclobutane ([4]aneNO); azaoxacyclopentane ([5]aneNO); azaoxacyclohexane ([6]aneNO); azaoxacycloheptane ([7]aneNO); azaoxacyclooctane ([8]aneNO); azaoxacyclobutene ([4]eneNO); azaoxacyclopentene ([5]eneNO); azaoxacyclohexene ([6]eneNO); azaoxacycloheptene ([7]eneNO); azaoxacyclooctene ([8]eneNO); azaoxacyclobutadiene ([4]dieneNO); azaoxacyclopentadiene ([5]dieneNO); azaoxacyclohexadiene ([6]dieneNO); azaoxacycloheptadiene ([7]dieneNO); azaoxacyclooctadiene ([8]dieneNO); diazaoxacyclohexane ([6]aneON2); diazaoxacycloheptane ([7]aneON2); diazaoxacyclooctane ([8]aneON2); diazaoxacyclononane ([9]aneON2); diazaoxacyclodecane ([10]aneON2); diazaoxacycloundecane ([11]aneON2); diazaoxacyclododecane ([12]aneON2); diazaoxacyclohexene ([6]eneON2); diazaoxacycloheptene ([7]eneON2); diazaoxacyclooctene ([8]eneON2); diazaoxacyclononene ([9]eneON2); diazaoxacyclodecene ([10]eneON2); diazaoxacycloundecene ([11]eneON2); diazaoxacyclododecene ([12]eneON2); diazadioxacyclooctane ([8]aneO2N2); diazadioxacyclononane ([9]aneO2N2); diazadioxacyclodecane ([10]aneO2N2); diazadioxacycloundecane ([11]aneO2N2); diazadioxacyclododecane ([12]aneO2N2); diazadioxacyclotridecane ([13]aneO2N2); diazadioxacyclotetradecane ([14]aneO2N2); diazadioxacyclopentadecane ([15]aneO2N2); diazadioxacyclohexadecane ([16]aneO2N2); diazadioxacycloheptadecane ([17]aneO2N2); diazadioxacyclooctadecane ([18]aneO2N2); diazadioxacyclononadecane ([19]aneON2); diazadioxacycloeicosane ([20]aneO2N2); diazadioxacyclooctadiene ([8]dieneO2N2); diazadioxacyclononadiene ([9]dieneO2N2); diazadioxacyclodecadiene ([10]dieneO2N2); diazadioxacycloundecadiene ([11]dieneO2N2); diazadioxacyclododecadiene ([12]dieneO2N2); diazadioxacyclotridecadiene ([13]dieneO2N2); diazadioxacyclotetradecadiene ([14]dieneO2N2); diazadioxacyclopentadecadiene ([15]dieneO2N2); diazadioxacyclohexadecadiene ([16]dieneO2N2); diazadioxacycloheptadecadiene ([17]dieneO2N2); diazadioxacyclooctadecadiene ([18]dieneO2N2); diazadioxacyclononadecadiene ([19]dieneO2N2); and diazadioxacycloeicosadiene ([20]dieneO2N2).
[0337] N—O Valence Stabilizer #50: Examples of four-, six-, eight-, or ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen or oxygen and are contained in component heterocyclic rings (N—O Bidentates, N—O Tridentates, N—O Tetradentates, or N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dipyrandipyridines; difurandipyrroles; tripyrantripyridines; trifurantripyrroles; tetrapyrantetrapyridines; and tetrafurantetrapyrroles.
[0338] N—O Valence Stabilizer #51: Examples of four-, six-, eight-, or ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen or oxygen and are contained in a combination of heterocyclic rings and amine, imine, hydroxy, carboxy, or carbonyl groups (N—O Bidentates, N—O Tridentates, N—O Tetradentates, or N—O Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: azaoxatetraphyrins; diazadioxatetraphyrins; azaoxahexaphyrins; diazadioxahexaphyrins; and triazatrioxahexaphyrins.
[0339] S—O Valence Stabilizer #1: Examples of 1,3-monothioketones (monothio-beta-ketonates), 1,3,5-monothioketones, 1,3,5-dithioketones, bis(1,3-monothioketones), and poly(1,3-monothioketones) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: hexafluoropenta-2-thione-4-ketone; 1,3-diphenyl-1,3-propana-1-thione-3-ketone; benzoylthiopinacolone; cyclohexoylthiocyclohexoylmethane; diphenylpentanedithionate; tetramethylnonanedithionate; hexafluoroheptanedithionate; trifluoroheptanedithionate; 1-(2-thienyl)-butan-1-thione-3-ketone, 1-(2-naphthyl)-butan-1-thione-3-ketone, and trifluoroacetylthiocamphor.
[0340] S—O Valence Stabilizer #2: Examples of thiomalonamides (thiomalonodiamides), bis(thiomalonamides), and polythiomalonamides (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: thiomalonamide, N-phenylthiomalonamide, N-benzylthiomalonamide, N-pentafluorophenylthiomalonamide, N-cyclohexylthiomalonamide, N-norbornylthiomalonamide, N,N′-diphenylthiomalonamide, N,N′-dibenzylthiomalonamide, N,N′-dipentafluorophenylthiomalonamide, N,N′-dicyclohexylthiomalonamide, and N,N′-norbornylthiomalonamide.
[0341] S—O Valence Stabilizer #3: Examples of 2-thioacylacetamides, 2-acylthioacetamides, bis(2-thioacylacetamides), bis(2acylthioacetamides), poly(2-thioacylacetamides), and poly(2-Acylthioacetamides) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-acetothioacetamide, 2-thioacetoacetamide, N-phenyl-2-acetothioacetamide, N-pentafluorophenyl-2-acetothioacetamide, N-benzyl-2-acetothioacetamide, N-cyclohexyl-2-acetothioacetamide, N-norbornyl-2-acetothioacetamide, N-phenyl-2-benzothioacetamide, N-pentafluorophenyl-2-pentafluorobenzothioacetamide, and N-cyclohexyl-2-cyclohexothioacetamide.
[0342] S—O Valence Stabilizer #4: Examples of dithiodicarbonic diamides, bis(dithiodicarbonic diamides), and poly(dithiodicarbonic diamides) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiodicarbonic diamide; N-phenyldithiodicarbonic diamide; N-pentafluorophenyldithiodicarbonic diamide; N-benzyldithiodicarbonic diamide; N-cyclohexyldithiodicarbonic diamide; N-norbornyldithiodicarbonic diamide; N,N′-diphenyldithiodicarbonic diamide; N,N′-dipentafluorophenyldithiodicarbonic diamide; N,N′-dibenzyldithiodicarbonic diamide; N,N′-dicyclohexyldithiodicarbonic diamide; and N,N′-dinorbornyldithiodicarbonic diamide.
[0343] S—O Valence Stabilizer #5: Examples of monothiohypophosphoric acids, bis(monothiohypophosphoric acids), poly(monothiohypophosphoric acids), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: monothiohypophosphoric acid, methylmonothiohypophosphoric acid, isopropylmonothiohypophosphoric acid, tert-butylmonothiohypophosphoric acid, phenylmonothiohypophosphoric acid, pentafluorophenylmonothiohypophosphoric acid, benzylmonothiohypophosphoric acid, cyclohexylmonothiohypophosphoric acid, norbornylmonothiohypophosphoric acid, dimethylmonothiohypophosphoric acid, diisopropylmonothiohypophosphoric acid, di-tert-butylmonothiohypophosphoric acid, diphenylmonothiohypophosphoric acid, di-pentafluorophenylmonothiohypophosphoric acid, dibenzylmonothiohypophosphoric acid, dicyclohexylmonothiohypophosphoric acid, and dinorbornylmonothiohypophosphoric acid.
[0344] S—O Valence Stabilizer #6: Examples of monothiohypophosphoramides, bis(monothiohypophosphoramides), and poly(monothiohypophosphoramides) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: monothiohypophosphoramide, N-methylmonothiohypophosphoramide, N-isopropylmonothiohypophosphoramide, N-tert-butylmonothiohypophosphoramide, N-phenylmonothiohypophosphoramide, N-pentafluorophenylmonothiohypophosphoramide, N-benzylmonothiohypophosphoramide, N-cyclohexylmonothiohypophosphoramide, N-norbornylmonothiohypophosphoramide, N,N′″-dimethylmonothiohypophosphoramide, N,N′″-diisopropylmonothiohypophosphoramide, N,N′″-di-tert-butylmonothiohypophosphoramide, N,N′″-diphenylmonothiohypophosphoramide, N,N′″-di-pentafluorophenylmonothiohypophosphoramide, N,N′″-dibenzylmonothiohypophosphoramide, N,N′″-dicyclohexylmonothiohypophosphoramide, and N,N″-dinorbornylmonothiohypophosphoramide.
[0345] S—O Valence Stabilizer #7: Examples of monothioimidodiphosphoric acids, monothiohydrazidodiphosphoric acids, bis(monothioimidodiphosphoric acids), bis(monothiohydrazidodiphosphoric acids), poly(monothioimidodiphosphoric acids), poly(monothiohydrazidodiphosphoric acids), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: monothioimidodiphosphoric acid, methylmonothioimidodiphosphoric acid, isopropylmonothioimidodiphosphoric acid, tert-butylnonothioimidodiphosphoric acid, phenylmonothioimidodiphosphoric acid, pentafluorophenylmonothioimidodiphosphoric acid, benzylmonothioimidodiphosphoric acid, cyclohexylmonothioimidodiphosphoric acid, norbornylmonothioimidodiphosphoric acid, dimethylmonothioimidodiphosphoric acid, diisopropylmonothioimidodiphosphoric acid, di-tert-butylmonothioimidodiphosphoric acid, diphenylmonothioimidodiphosphoric acid, di-pentafluorophenylmonothioimidodiphosphoric acid, dibenzylmonothioimidodiphosphoric acid, dicyclohexylmonothioimidodiphosphoric acid, and dinorbornylmonothioimidodiphosphoric acid.
[0346] S—O Valence Stabilizer #8: Examples of monothioimidodiphosphoramides, monothiohydrazidodiphosphoramides, bis(monothioimidodiphosphoramides), bis(monothiohydrazidodiphosphoramides), poly(monothioimidodiphosphoramides), and poly(monothiohydrazidodiphosphoramides) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: monothioimidodiphosphoramide, N-methylmonothioimidodiphosphoramide, N-isopropylmonothioimidodiphosphoramide, N-tert-butylmonothioimidodiphosphoramide, N-phenylmonothioimidodiphosphoramide, N-pentafluorophenylmonothioimidodiphosphoramide, N-benzylmonothioimidodiphosphoramide, N-cyclohexylmonothioimidodiphosphoramide, N-norbornylmonothioimidodiphosphoramide, N,N′″-dimethylmonothioimidodiphosphoramide, N,N′″-diisopropylmonothioimidodiphosphoramide, N,N′″-di-tert-butylmonothioimidodiphosphoramide, N,N′″-diphenylmonothioimidodiphosphoramide, N,N′″-di-pentafluorophenylmonothioimidodiphosphoramide, N,N′″-dibenzylmonothioimidodiphosphoramide, N,N′″-dicyclohexylmonothioimidodiphosphoramide, and N,N′″-dinorbornylmonothioimidodiphosphoramide.
[0347] S—O Valence Stabilizer #9: Examples of monothiodiphosphoramides, bis(monothiodiphosphoramides), and poly(monothiodiphosphoramides) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: monothiodiphosphoramide, N-methylmonothiodipbosphoramide, N-isopropylmonothiodiphosphoramide, N-tert-butylmonothiodiphosphoramide, N-phenylmonothiodiphosphoramide, N-pentafluorophenylmonothiodiphosphoramide, N-benzylmonothiodiphosphoramide, N-cyclohexylmonothiodiphosphoramide, N-norbornylmonothiodiphosphoramide, N,N′″-dimethylmonothiodiphosphoramide, N,N′″-diisopropylmonotbiodiphosphoramide, N,N′″-di-tert-butylmonothiodiphosphoramide, N,N′″-diphenylmonothiodiphosphoramide, N,N′″-di-pentafluorophenylmonothiodiphosphoramide, N,N′″-dibenzylmonothiodiphosphoramide, N,N′″-dicyclohexylmonothiodiphosphoramide, and N,N′″-dinorbornylmonothiodiphosphoramide.
[0348] S—O Valence Stabilizer #10: Examples of monothiodiphosphoric acids, bis(monotbiodiphosphoric acids), poly(monothiodiphosphoric acids), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: monothiodiphosphoric acid, methylmonothiodiphosphoric acid, isopropylmonothiodiphosphoric acid, tert-butylmonothiodiphosphoric acid, phenylmonothiodiphosphoric acid, pentafluorophenylmonothiodiphosphoric acid, benzylmonothiodiphosphoric acid, cyclohexylmonothiodiphosphoric acid, norbornylmonothiodiphosphoric acid, dimethylmonothiodiphosphoric acid, diisopropylmonothiodiphosphoric acid, di-tert-butylmonothiodiphosphoric acid, diphenylmonothiodiphosphoric acid, di-pentafluorophenylmonothiodiphosphoric acid, dibenzylmonothiodiphosphoric acid, dicyclohexylmonothiodiphospboric acid, and dinorbornylmonothiodiphosphoric acid.
[0349] S—O Valence Stabilizer #11: Examples of monothiocarbamates, bis(monothiocarbamates), and poly(monothiocarbamates) (including N-hydroxymonothiocarbamates and N-mercaptomonothiocarbamates) (S—O Bidentates, S—O Tridentates, and S—O Tetradentates) that rmeet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dimethylmonothiocarbamate (dmmtc); di(trifluorodimethyl)monothiocarbamate; diethylmonothiocarbamate (demtc); dipropylmonothiocarbamate; diisopropylmonothiocarbamate; dibutylmonothiocarbamate; ditertbutylmonothiocarbamate; dicyanamidomonothiocarbamate; diphenylmonothiocarbamate; di(pentafluorophenyl)monothiocarbamate; dibenzylmonothiocarbamate; dinaphthylmonothiocarbamate; dicyclohexylmonothiocarbamate; dinorbornylmonothiocarbamate; diadamantylmonothiocarbamate; pyrrolidinomonothiocarbamate (pyrmtc); piperidinomonothiocarbamate (pipmtc); morpholinomonothiocarbamate (mormtc); thiamorpholinomonothiocarbamate; 3-pyrrolinomonothiocarbamate; pyrrolomonothiocarbamate; oxazolomonothiocarbamate; isoxazolomonothiocarbamate; thiazolomonothiocarbamate; isothiazolomonothiocarbamate; indolomonothiocarbamate; carbazolomonothiocarbamate; pyrazolinomonothiocarbamate; imidazolinomonothiocarbamate; pyrazolomonothiocarbamate; imidazolomonothiocarbamate; indazolomonothiocarbamate; and triazolomonothiocarbamate.
[0350] Miscellaneous Valence Stabilizer #1: Examples of hydroxo and oxo functionalities that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: water (H2O); dioxygen (O2); oxide (O2−); hydroxide (OH−); peroxo groups (O22−); and superoxo groups (O2−).
[0351] As with the inorganic valence stabilizers, crosses between two or more organic stabilizers can be used. For example, in some instances it may be desirable to form a valence stabilizer out of a nitrogen-containing heterocyclic and an amine ligand. During the synthesis process, both of these materials will complex with the MnIII or MnIV ion to produce a mixed nitrogen heterocyclic/amine valence stabilizer compound from the pigment solution.
[0352] 3c) Narrow Band Inorganic Valence Stabilizers
[0353] Additional valence stabilizers can be used in conjunction with the MnIII and MnIV ions for corrosion protection. However, these less typical stabilizers suffer from disadvantages that make their selection over the previously mentioned wide band valence stabilizers less desirable. For this reason, we term them “narrow band” valence stabilizers because of their limited applications. Narrow band stabilizers exhibit some limitation in their use when compared to wide band stabilizers. Narrow band inorganic stabilizers may be toxic or may complex MnII or MnIV only with difficulty. These narrow band stabilizers include, but are not limited to, bismuthates, gennanates, arsenates, and carbonates. For example, valence stabilizers using arsenate are less desirable because their inherent toxicity is very large (greater than PbIV or CrVI), although they may be very effective at inhibiting corrosion when used with MnII. Arsenates could be used as MnIII valence stabilizers in situations where the toxicity of the pigment is not a factor in its use.
[0354] Modifications of wide band inorganic valence stabilizers can result in a complex with reduced corrosion inhibition. The central cavity of the heteropolymetallates can contain ions in addition to the desired MnIII or MnIV ion. For example, the use of silicomolybdates, phosphomolybdates, silicotungstates, and phosphotungstates is possible. In these MnIII- or MnIV-valence stabilizer complexes, Si+4 or P+5 ions also occupy the central cavity of the complex with the MnIII or MnIV ion. The inclusion of additional ions in the central cavity reduces the stability of the complex, and thereby leads to lower corrosion protection. Nonetheless, these complexes also demonstrate some corrosion inhibiting activity. The additional ions that can be included within the central cavity of the heteropolymetallates described above depend upon the size of the central cavity, which in turn depends upon the specific chemistry exhibited by an inorganic valence stabilizer (e.g., molybdate, tungstate, periodate, etc.) In general, these additional ions must also be small so as to ensure the stability of the formed MnIII- or MnIV-valence stabilized complex. Examples of small additional ions include, but are not limited to: B+3, Al+3, Si+4, P+5, Ti+4, V+5, V+4, Cr+6, Cr+3, Mn+2, Fe+3, Fe+2, CO+3, CO+2, Ni+2, N+3, Ni+4, CU+2, Cu+3, Zn+2, Ga+3, Ge+4, AS+5, As+3, Zr+4, and Ce+4.
[0355] Water-soluble precursors for these materials are desirable. Typically, the free acids (e.g., silicomolybdic acid, phosphotungstic acid, borotungstic acid, etc.) offer the most water-soluble precursors for these materials.
[0356] 3d) Narrow Band Organic Valence Stabilizers
[0357] Narrow band organic valence:stabilizers include those general classes of chemical compounds that result in MnIII- or MnIV-valence stabilizer compounds that are either less stable, more soluble in water, or more toxic than the wide band organic stabilizers. 6 TABLE 5 Narrow Band Organic Valence Stabilizers for the Mn+3 and Mn+4 Ions General Structural Name (Type of Organic) Structural Representation N Valence Stabilizer #1: Macrocyclic ligands containing five, seven, or Five-, Seven-, or Nine-Membered nine nitrogen binding sites to valence stabilize Macrocyclics, Macrobicyclics, and the central metal ion. Can include other Macropolycyclics (including Catapinands, hydrocarbon or ring systems bound to this Cryptands, Cyclidenes, and Sepulchrates) macrocyclic ligand, but they do not coordinate wherein all Binding Sites are composed of with the stabilized, high valence metal ion. This Nitrogen (usually amine or imine groups) ligand and/or attached, uncoordinating and are not contained in Component hydrocarbons/rings may or may not have Heterocyclic Rings (N—N Tridentates, N—N halogen or polarizing or water- Tetradentates, and N—N Hexadentates) insolubilizing/solubilizing groups attached. N Valence Stabilizer #2: Macrocyclic ligands containing a total of five or Five-, or Seven-Membered Macrocyclics, seven five-membered heterocyclic rings Macrobicyclics, and Macropolycyclics containing nitrogen binding sites. Can include (including Catapinands, Cryptands, other hydrocarbon/ring systems bound to this Cyclidenes, and Sepulchrates) wherein all macrocyclic ligand, but they do not coordinate Binding Sites are composed of Nitrogen with the stabilized, high valence metal ion. This and are contained in Component 5- ligand and/or attached, uncoordinating Membered Heterocyclic Rings (N—N hydrocarbon/rings may or may not have halogen Tridentates, N—N Tetradentates, or N—N or polarizing or water-insolubilizing groups Hexadentates) attached. N Valence Stabilizer #3: Macrocyclic ligands containing at least one 5- Five-, Seven-, or Nine-Membered membered heterocyclic ring. These Macrocyclics, Macrobicyclics, and heterocyclic rings provide nitrogen binding sites Macropolycyclics (including Catapinands, to valence stabilize the central metal ion. Other Cryptands, Cyclidenes, and Sepulchrates) amine or imine binding sites can also be wherein all Binding Sites are composed of included in the macrocyclic ligand, so long as Nitrogen and are contained in a the total number of binding sites is five, seven, Combination of 5-Membered Heterocyclic or nine. Can include other hydrocarbon/ring Rings and Amine or Imine Groups (N—N systems bound to this macrocyclic ligand, but Tridentates, N—N Tetradentates, or N—N they do not coordinate with the stabilized, high Hexadentates) valence metal ion. This ligand and/or attached, uncoordinating hydrocarbon/rings may or may not have halogen or polarizing or water- insolubilizing groups attached. N Valence Stabilizer #4: Macrocyclic ligands containing a total of five or Five- or Seven-Membered Macrocyclics, seven six-membered heterocyclic rings Macrobicyclics, and Macropolycyclics containing nitrogen binding sites. Can include (including Catapinands, Cryptands, other hydrocarbon/ring systems bound to this Cyclidenes, and Sepulchrates) wherein all macrocyclic ligand, but they do not coordinate Binding Sites are composed of Nitrogen with the stabilized, high valence metal ion. This and are contained in Component 6- ligand and/or attached, uncoordinating Membered Heterocyclic Rings (N—N hydrocarbon/rings may or may not have halogen Tridentates, N—N Tetradentates, or N—N or polarizing or water-insolubilizing groups Hexadentates) attached. N Valence Stabilizer #5: Macrocyclic ligands containing at least one 6- Five-, Seven-, or Nine-Membered membered heterocyclic ring. These Macrocyclics, Macrobicyclics, and heterocyclic rings provide nitrogen binding sites Macropolycyclics (including Catapinands, to valence stabilize the central metal ion. Other Cryptands, Cyclidenes, and Sepulchrates) amine or imine binding sites can also be wherein all Binding Sites are composed of included in the macrocyclic ligand, so long as Nitrogen and are contained in a the total number of binding sites is five, seven, Combination of 6-Membered Heterocyclic or nine. Can include other hydrocarbon/ring Rings and Amine or Imine Groups (N—N systems bound to this macrocyclic ligand, but Tridentates, N—N Tetradentates, or N—N they do not coordinate with the stabilized, high Hexadentates) valence metal ion. This ligand and/or attached, uncoordinating hydrocarbon/rings may or may not have halogen or polarizing or water- insolubilizing groups attached. N Valence Stabilizer #6: N(SiR3)3, R′N(SiR3)2, or R′R″N(SiR3) for Silylamines and Silazanes, including silylamines; and [RR″Si—NR′]x (x = 1-10) for Macrocyclic Derivatives, wherein at least silazanes where R, R′, and R″ represents H or one Nitrogen Atom is a Binding Site (N any organic functional group wherein the Monodentates, N—N Bidentates, N—N number of carbon atoms ranges from 0 to 35, Tridentates, N—N Tetradentates, and N—N optionally having halogen or polarizing or Hexadentates) water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, P, As, O, S, or Se atoms. N Valence Stabilizer #7: RR′—N—C(═NH)NR″R″′, where R, R′, R″, and Guanidines, Diguanidines, and R″′ represent H or any organic functional group Polyguanidines (N—N Bidentates, N—N wherein the number of carbon atoms ranges Tridentates, N—N Tetradentates, and N—N from 0 to 40, optionally having halogen or Hexadentates) polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #8: RR′—N—P(═N)—N—R″R″′, where R, R′, R″, and Phosphonitrile Amides, and R″′ represent H or any organic functional group Bis(phosphonitrile amides) (N—N wherein the number of carbon atoms ranges Bidentates, N—N Tetradentates) from 0 to 40, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #9: (NH═)PR″″(—NRR′)(—NR″R″′), where R, R′, Phosphonimidic Diamides, R″, R″′, and R″″ represent H or any organic Bis(Phosphonimidic Diamides), and functional group wherein the number of carbon Poly(Phosphonimidic Diamides) (N—N atoms ranges from 0 to 40, optionally having Bidentates, N—N Tetradentates) halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #10: (NH═)PR″′(—NRR′)(—OR″) for Phosphonamidimidic Acid, phosphonamidimidic acid and (NH═)PR″′(— Phosphonamidimidothioic Acid, NRR′)(—SR″) for phosphonamidimidothioic Bis(Phosphonamidimidic Acid), acid, where R, R′, R″, and R″′ represent H or Bis(Phosphonamidimidothioic Acid), any organic functional group wherein the Poly(Phosphonamidimidic Acid), number of carbon atoms ranges from 0 to 40, Poly(Phosphonamidimidothioic Acid), and optionally having halogen or polarizing or derivatives thereof (N—N Bidentates, and N— water-insolubilizing/solubilizing groups N Tetradentates) attached. Ligand can also contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #11: C5H5N—CR═NR′, where C5H5N is a pyridine Pyridinaldimines, Bis(pyridinaldimines), derivative, R is typically an aromatic constituent and Poly(pyridinaldimines) (N—N (i.e. —C6H5), and R′ represents H or any organic Bidentates, N—N Tridentates, and N—N functional group wherein the number of carbon Tetradentates) atoms ranges from 0 to 40, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #12: R—NH—N═R′, where R and R′ represent H or Hydrazones, Bis(hydrazones), and any organic functional group wherein the Poly(hydrazones) (N Monodentates, N—N number of carbon atoms ranges from 0 to 40, Bidentates, N—N Tridentates, and N—N optionally having halogen or polarizing or Tetradentates) water-insolubilizing/solubilizing groups attached. (Either R or R′ is typically an aryl group.) Ligand can also contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #13: R—N═N—R′ for azo compounds, R—N═N—NH—R′ Azo compounds including triazenes without for triazenes, where R, and R′ represent H or chelate substitution at the ortho- (for aryl) any organic functional group wherein the or alpha- or beta- (for alkyl) positions, number of carbon atoms ranges from 0 to 40, Bis(azo compounds), or Poly(azo optionally having halogen or polarizing or compounds) (N Monodentates, N—N water-insolubilizing/solubilizing groups Bidentates, or N—N—N Tridentates) attached. (Not including ortho- chelate substituted aryl azo compounds, and alpha- or beta-substituted alkyl azo compounds.) Ligand can also contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #14: R—N═N—CR′═N—NR″R″′, where R, R′, R″, and Formazans, Bis(formazans), and R″′ represent H, or any organic-functional Poly(formazans) without ortho- hydroxy, group wherein the number of carbon atoms carboxy, thiol, mercapto, amino, or ranges from 0 to 40, optionally having halogen hydrazido substitution (N—N Bidentates, N— or polarizing or water- N Tetradentates, and N—N Hexadentates) insolubilizing/solubilizing groups attached. (Not including ortho- hydroxy, carboxy, thiol, mercapto, amino, or hydrazido substitution.) Ligand can also contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #15: R—CH═N—CHR′—N═CHR″, where R, R′, and R″ Hydramides (N—N Bidentates) represent H, or any organic functional group wherein the number of carbon atoms ranges from 0 to 40, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. (R, R′, and R″ are typically aryl derivatives.) Ligand can also contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #16: RR′C═N—N═CR″R″′ or RR′C═N—NR″R″′ (for Azines (including ketazines), Bis(azines), ketazines), where R, R′, R″, and R″′ represent and Poly(azines) without ortho- hydroxy, H, or any organic functional group wherein the carboxy, thiol, mercapto, amino, or number of carbon atoms ranges from 0 to 40, hydrazido substitution (N—N Bidentates, N— optionally having halogen or polarizing or N Tetradentates, and N—N Hexadentates) water-insolubilizing/solubilizing groups attached. (Not including ortho- hydroxy, carboxy, thiol, mercapto, amino, or hydrazido substitution.) Ligand can also contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #17: RR′C═N—R″, where R, R′, and R″ represent H, Schiff Bases with one Imine (C═N) Group or any organic functional group wherein the and without ortho- (for aryl constituents) or number of carbon atoms ranges from 0 to 40, alpha- or beta- (for alkyl constituents) optionally having halogen or polarizing or hydroxy, carboxy, carbonyl, thiol, water-insolubilizing/solubilizing groups mercapto, thiocarbonyl, amino, imino, attached. (Not including ortho-, alpha-, or beta- oximo, diazeno, or hydrazido substitution hydroxy, carboxy, carbonyl, thiol, mercapto, (N Monodentates) thiocarbonyl, amino, imino, oximo, diazeno, or hydrazido substitution.) Ligand can also contain nonbinding N, O, S, or P atoms. N Valence Stabilizer #18: Isocyanides, cyanamides, and related ligands Isocyanide and Cyanamide and related where the nitrogen atom is directly complexed ligands (N Monodentates) to the high valence metal ion. N Valence Stabilizer #19: Nitrosyl, nitrite, and related ligands where the Nitrosyl and Nitrite and related ligands (N nitrogen atom is bound directly to the high Monodentates) valence metal ion. N Valence Stabilizer #20: R—CN, R—(CN)2, R—(CN)x, etc. where R Nitriles, Dinitriles, and Polynitriles (N represents H or any organic functional group Monodentates, N—N Bidentates, and N—N—N wherein the number of carbon atoms ranges Tridentates) from 0 to 40, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. N Valence Stabilizer #21: Azide (—N3) ligands bound directly to the high Azide ligands (N Monodentates, or N—N valence metal ion. Also includes organoazide Bidentates) derivatives (R—N3), triazenido compounds (R— N3—R′), phosphonyl azides (R—PO2H—N3), phosphoryl azides (O—PO2H—N3), and sulfonyl azides (R—SO2—N3) where R and R′ represent H or any organic functional group wherein the number of carbon atoms ranges from 0 to 35, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached S Valence Stabilizer #1: SH2, SHR, SR2, where R represents H or any Monothioethers (S Monodentates) wherein organic functional group wherein the number of at least one Sulfur Atom is a Binding Site carbon atoms ranges from 0 to 35, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, P, O, S, or Se atoms. S Valence Stabilizer #2: R—S—S—R′, where R and R′ represents H or any Disulfides (S Monodentates) wherein at organic functional group wherein the number of least one Sulfur Atom is a Binding Site carbon atoms ranges from 0 to 35, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, P, O, S, or Se atoms. S Valence Stabilizer #3: R—S—R′—S—R″, where R, R′, and R″ represents H Dithioethers (S—S Bidentates) wherein at or any organic functional group wherein the least one Sulfur Atom is a Binding Site number of carbon atoms ranges from 0 to 35, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, P, O, S, or Se atoms. S Valence Stabilizer #4: R—S—R′—S—R″—S—R″′, where R, R′, R″, and R″′ Trithioethers (S—S Bidentates or S—S represents H or any organic functional group Tridentates) wherein at least one Sulfur wherein the number of carbon atoms ranges Atom is a Binding Site from 0 to 35, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, P, O, S, or Se atoms. S Valence Stabilizer #5: R—S—R′—S—R″—S—R″′—S—R″″, where R, R′, R″, Tetrathioethers (S—S Bidentates, S—S R″′, and R″″ represents H or any organic Tridentates, or S—S Bidentates) wherein at functional group wherein the number of carbon least one Sulfur Atom is a Binding Site atoms ranges from 0 to 35, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, P, O, S, or Se atoms. S Valence Stabilizer #6: R—S—R′—S—R″—S—R″′—S—R″″—S—R″″′—S—R″″″, Hexathioethers (S—S Bidentates, S—S where R, R′, R″, R″′, R″″, R″″′, and R″″″ Tridentates, S—S Tetradentates, or S—S represents H or any organic functional group Hexadentates) wherein at least one Sulfur wherein the number of carbon atoms ranges Atom is a Binding Site from 0 to 35, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, P, O, S, or Se atoms. S Valence Stabilizer #7: Five membered heterocyclic ring containing one Five-Membered Heterocyclic Rings or two sulfur atoms, both of which may function containing One or Two Sulfur Atoms as binding sites. Can include other ring systems wherein at least one Sulfur Atom is a bound to this heterocyclic ring, but they do not Binding Site (S Monodentates or S—S coordinate with the stabilized, high valence Bidentates) metal ion. Ring can also contain O, N, P, As, or Se atoms. This 5-membered ring and/or attached, uncoordinating rings may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. S Valence Stabilizer #8: Six membered heterocyclic ring containing just Six-Membered Heterocyclic Rings one or two sulfur atoms, both of which may containing One or Two Sulfur Atoms function as binding sites. Can include other wherein at least one Sulfur Atom is a ring systems bound to this heterocyclic ring, but Binding Site (S Monodentates or S—S they do not coordinate with the stabilized, high Bidentates) valence metal ion. Ring can also contain O, N, P, As, or Se atoms. This 5-membered ring and/or attached, uncoordinating rings may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. S Valence Stabilizer #9: Five membered heterocyclic ring(s) containing Five-Membered Heterocyclic Rings one or two sulfur atoms. In addition, ligand containing One or Two Sulfur Atoms at contains additional sulfur-containing least one additional Sulfur Atom Binding substituents (usually thiols or thioethers) that Site not in a Ring (S Monodentates, S—S constitute S binding sites. Can include other Bidentates, S—S Tridentates, S—S ring systems bound to the heterocyclic ring or to Tetradentates, or S—S Hexadentates) the S-containing substituent, but they do not coordinate with the stabilized, high valence metal ion. Ring(s) can also contain O, N, P, As or Se atoms. This 5-membered ring(s) and/or attached, uncoordinating rings and/or S- containing substituent(s) may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. S Valence Stabilizer #10: Six membered heterocyclic ring(s) containing Six-Membered Heterocyclic Rings one or two sulfur atoms. In addition, ligand containing One or Two Sulfur Atoms at contains additional sulfur-containing least one additional Sulfur Atom Binding substituents (usually thiols or thioethers) that Site not in a Ring (S Monodentates, S—S constitute S binding sites. Can include other Bidentates, S—S Tridentates, S—S ring systems bound to the heterocyclic ring or to Tetradentates, or S—S Hexadentates) the S-containing substituent, but they do not coordinate with the stabilized, high valence metal ion. Ring(s) can also contain O, N, P, As or Se atoms. This 6-membered ring(s) and/or attached, uncoordinating rings and/or S- containing substituent(s) may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. S Valence Stabilizer #11: Five membered heterocyclic ring(s) containing Five-Membered Heterocyclic Rings one or two sulfur atoms. In addition, ligand containing One or Two Sulfur Atoms at contains additional sulfur-containing rings that least one additional Sulfur Atom Binding constitute S binding sites. Can include other Site in a separate Ring (S Monodentates, S— ring systems bound to the S-containing S Bidentates, S—S Tridentates, S—S heterocyclic rings, but they do not coordinate Tetradentates, or S—S Hexadentates) with the stabilized, high valence metal ion. Ring(s) can also contain O, N, P, As, or Se atoms. This 5-membered ring(s) and/or additional S-containing ring(s) and/or attached, uncoordinating rings may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. S Valence Stabilizer #12: Six membered heterocyclic ring(s) containing Six-Membered Heterocyclic Rings one or two sulfur atoms. In addition, ligand containing One or Two Sulfur Atoms at contains additional sulfur-containing rings that least one additional Sulfur Atom Binding constitute S binding sites. Can include other Site in a separate Ring (S Monodentates, S— ring systems bound to the S-containing S Bidentates, S—S Tridentates, S—S heterocyclic rings, but they do not coordinate Tetradentates, or S—S Hexadentates) with the stabilized, high valence metal ion. Ring(s) can also contain O, N, P, As, or Se atoms. This 6-membered ring(s) and/or additional S-containing ring(s) and/or attached, uncoordinating rings may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. S Valence Stabilizer #13: Macrocyclic ligands containing two to ten sulfur Two-, Three-, Four-, Five-, Six-, Seven-, binding sites to valence stabilize the central Eight-, Nine-, and Ten-Membered metal ion. Can include other hydrocarbon or Macrocyclics, Macrobicyclics, and ring systems bound to this macrocyclic ligand, Macropolycyclics (including Catapinands, but they do not coordinate with the stabilized, Cryptands, Cyclidenes, and Sepulchrates) high valence metal ion. This ligand and/or wherein all Binding Sites are composed of attached, uncoordinating hydrocarbons/rings Sulfur (usually thiol or thioether groups) may or may not have halogen or polarizing or and are not contained in Component water-insolubilizing/solubilizing groups Heterocyclic Rings (S—S Bidentates, S—S attached. Tridentates, S—S Tetradentates, and S—S Hexadentates) S Valence Stabilizer #14: Macrocyclic ligands containing a total of four to Four-, Five-, Six-, Seven-, Eight-, Nine-, or ten five-membered heterocyclic rings containing Ten-Membered Macrocyclics, sulfur binding sites. Can include other Macrobicyclics, and Macropolycyclics hydrocarbon/ring systems bound to this (including Catapinands, Cryptands, macrocyclic ligand, but they do not coordinate Cyclidenes, and Sepulchrates) wherein all with the stabilized, high valence metal ion. This Binding Sites are composed of Sulfur and ligand and/or attached, uncoordinating are contained in Component 5-Membered hydrocarbon/rings may or may not have halogen Heterocyclic Rings (S—S Tridentates, S—S or polarizing or water-insolubilizing groups Tetradentates or S—S Hexadentates) attached. S Valence Stabilizer #15: Macrocyclic ligands containing at least one 5- Four-, Five-, Six-, Seven-, Eight-, Nine-, or membered heterocyclic ring. These Ten-Membered Macrocyclics, heterocyclic rings provide sulfur binding sites to Macrobicyclics, and Macropolycyclics valence stabilize the central metal ion. Other (including Catapinands, Cryptands, thiol, thioether, or thioketo binding sites can Cyclidenes, and Sepulchrates) wherein all also be included in the macrocyclic ligand, so Binding Sites are composed of Sulfur and long as the total number of binding sites is four are contained in a Combination of 5- to ten. Can include other hydrocarbon/ring Membered Heterocyclic Rings and Thiol, systems bound to this macrocyclic ligand, but Thioether, or Thioketo Groups (S—S they do not coordinate with the stabilized, high Tridentates, S—S Tetradentates, or S—S valence metal ion. This ligand and/or attached, Hexadentates) uncoordinating hydrocarbon/rings may or may not have halogen or polarizing or water- insolubilizing groups attached. S Valence Stabilizer #16: Macrocyclic ligands containing a total of four to Four-, Five-, Six-, Seven-, Eight-, Nine-, or ten six-membered heterocyclic rings containing Ten-Membered Macrocyclics, sulfur binding sites. Can include other Macrobicyclics, and Macropolycyclics hydrocarbon/ring systems bound to this (including Catapinands, Cryptands, macrocyclic ligand, but they do not coordinate Cyclidenes, and Sepulchrates) wherein all with the stabilized, high valence metal ion. This Binding Sites are composed of Sulfur and ligand and/or attached, uncoordinating are contained in Component 6-Membered hydrocarbon/rings may or may not have halogen Heterocyclic Rings (S—S Tridentates, S—S or polarizing or water-insolubilizing groups Tetradentates, or S—S Hexadentates) attached. S Valence Stabilizer #17: Macrocyclic ligands containing at least one 6- Four-, Five-, Six-, Seven-, Eight-, Nine-, or membered heterocyclic ring. These Ten-Membered Macrocyclics, heterocyclic rings provide sulfur binding sites to Macrobicyclics, and Macropolycyclics valence stabilize the central metal ion. Other (including Catapinands, Cryptands, thiol, thioether, or thioketo binding sites can Cyclidenes, and Sepulchrates) wherein all also be included in the macrocyclic ligand, so Binding Sites are composed of Sulfur and long as the total number of binding sites is four are contained in a Combination of 6- to ten. Can include other hydrocarbon/ring Membered Heterocyclic Rings and Thiol, systems bound to this macrocyclic ligand, but Thioether, or Thioketo Groups (S—S they do not coordinate with the stabilized, high Tridentates, S—S Tetradentates, or S—S valence metal ion. This ligand and/or attached, Hexadentates) uncoordinating hydrocarbon/rings may or may not have halogen or polarizing or water- insolubilizing groups attached. S Valence Stabilizer #18: RR′—N—C(═S)—NR″—C(═S)—NR″′R″″ for Dithiobiurets (Dithioimidodicarbonic dithiobiurets, and RR′—N—C(═S)—NR″—NH— Diamides), Dithioisobiurets, Dithiobiureas, C(═S)—NR″′R″″ for dithiobiureas, where R, R′, Trithiotriurets, Trithiotriureas, R″, R″′, and R″″ represent H, NH2, or any Bis(dithiobiurets), Bis(dithioisobiurets), organic functional group wherein the number of Bis(dithiobiureas), Poly(dithiobiurets), carbon atoms ranges from 0 to 40, optionally Poly(dithioisobiurets), and having halogen or polarizing or water- Poly(dithiobiureas) (S—S Bidentates, S—S insolubilizing/solubilizing groups attached. Tridentates, S—S Tetradentates) Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #19: RR′—N—C(═S)—NR″—C(═S)—R″′ where R, R′, R″, Thioacylthioureas, Thioaroylthioureas, and R″′ represent H, NH2, or any organic Bis(thioacylthioureas), functional group wherein the number of carbon Bis(thioaroylthioureas), atoms ranges from 0 to 40, optionally having Poly(thioacylthioureas), and halogen or polarizing or water- Poly(thioaroylthioureas) (S—S Bidentates, S— insolubilizing/solubilizing groups attached. S Tridentates, S—S Tetradentates) Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #20: R—C(═S)—S—S—C—(═S)—R′ where R, and R′ Dithioacyl disulfides, Bis(dithioacyl represent H or any organic functional group disulfides), and Poly(dithioacyl disulfides) wherein the number of carbon atoms ranges (S—S Bidentates, S—S Tridentates, S—S from 0 to 40, optionally having halogen or Tetradentates) polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #21: RR′—N—C(═S)—S—S—C(═S)—N—R″R″′ where R, R′, Tetrathioperoxydicarbonic Diamides, R″, R″′ represent H or any organic functional Bis(tetrathioperoxydicarbonic diamides), group wherein the number of carbon atoms and poly(tetrathioperoxydicarbonic ranges from 0 to 40, optionally having halogen diamides) (S—S Bidentates, S—S Tridentates, or polarizing or water- S—S Tetradentates) insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #22: R—S—C(═S)—S—S—C(═S)—S—R′ for Hexathio-, Pentathio-, and hexathioperoxydicarbonic acids, R—O—C(═S)—S— Tetrathioperoxydicarbonic Acids, S—C(═S)—S—R′ for pentathioperoxydicarbonic Bis(hexathio-, pentathio-, and acids, and R—O—C(═S)—S—S—C(═S)—O—R′ for tetrathioperoxydicarbonic acids), tetrathioperoxydicarbonic acids, where R and R′ poly(hexathio-, pentathio-, and represent H, NH2 or any organic functional tetrathioperoxydicarbonic acids), and group wherein the number of carbon atoms derivatives thereof (S—S Bidentates, S—S ranges from 0 to 40, optionally having halogen Tridentates, S—S Tetradentates) or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #23: (RR′—N—)(RR″R″′—N—)P(═S)—S—S—P(═S)(—N— Dithioperoxydiphosphoramide, R″″R″″′)(—N—R″″″R″″″′), where R, R′, R″, R″′, Bis(dithioperoxyphosphoramide), and R″″, R″″′, R″″″, and R″″″′ represent H, NH2 or Poly(dithioperoxydiphosphoramide) (S—S any organic functional group wherein the Bidentates, S—S Tridentates, S—S number of carbon atoms ranges from 0 to 40, Tetradentates) optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #24: (R—O—)(R′—O—)P(═S)—S—S—P(═S)(—O—R″)(—O— Dithioperoxydiphosphoric Acids, R″′); (R—O—)(R′—S—)P(═S)—S—S—P(═S)(—S—R″)(—O— Bis(dithioperoxyphosphoric Acids), R″′); or (R—S—)(R′—S—)P(═S)—S—S—P(═S)(—S—R″)(— Poly(dithioperoxydiphosphoric Acids), and S—R″′), where R, R′, R″, R″′, R″″, R″″′, R″″″, derivatives thereof (S—S Bidentates, S—S and R″″″′ represent H, NH2 or any organic Tridentates, S—S Tetradentates) functional group wherein the number of carbon atoms ranges from 0 to 40, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #25: (R—O—)(R′—)P(═S)—NH—P(═S)(—R″)(—O—R″′); (R— Dithioimidodiphosphonic Acids, S—)(R′—)P(═S)—NH—P(═S)(—R″)(—O—R″′); or (R— Dithiohydrazidodiphosphonic Acids, S—)(R′—)P(═S)—NH—P(═S)(—R″)(—S—R″′) for Bis(dithioimidodiphosphonic acids), dithioimidodiphosphonic acids, and —NH—NH— Bis(dithiohydrazidodiphosphonic acids), derivatives for dithiohydrazidodiphosphonic Poly(dithioimidodiphosphonic acids), acids, where R, R′, R″, and R″′ represent H, Poly(dithiohydrazidodiphosphonic acids), NH2 or any organic functional group wherein and derivatives thereof (S—S Bidentates, S—S the number of carbon atoms ranges from 0 to Tridentates, and S—S Tetradentates) 40, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #26: (RR′—N—)(R″—)P(═S)—NH—P(═S)(—R″′)(—N— Dithioimidodiphosphonamides, R″″R″″′) for dithioimidophosphonamides, and Dithiohydrazidodiphosphonamides, (RR′—N—)(R″—)P(═S)—NH—NH—P(═S)(—R″′)(—N— Bis(dithioimidodiphosphonamides), R″″R″″′) for Bis(dithiohydrazidodiphosphonamides), dithiohydrazidodiphosphonamides, where R, R′, Poly(dithioimidodiphosphonamides), and R″, R″′, R″″, and R″″′ represent H, NH2 or any Poly(dithiohydrazidodiphosphonamides) organic functional group wherein the number of (S—S Bidentates, S—S Tridentates, S—S carbon atoms ranges from 0 to 40, optionally Tetradentates) having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #27: (RR′—N—)(R″—)P(═S)—S—P(═S)(—R″′)(—N— Dithiodiphosphonamides, R″″R″″′), or (RR′—N—)(R″—)p(═S)—O—P—(═S)(— Bis(dithiophosphonamides), and R″′)(—N—R″″R″″′), where R, R′, R″, R″′, R″″, Poly(dithiodiphosphonamides) (S—S and R″″′ represent H, NH2 or any organic Bidentates, S—S Tridentates, S—S functional group wherein the number of carbon Tetradentates) atoms ranges from 0 to 40, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #28: (R—O—)(R′—)P(═S)—O—P(═S)(—R″)(—O—R″′); (R—O—) Dithiodiphosphonic Acids, (R′—)P(═S)—S—P(═S)(—R″)(—O—R″′); (R—S—)(R′—) Bis(dithioiphosphonic Acids), P(═S)—O—P(═S)(—R″)(—S—R″′); or (R—S—)(R′—) Poly(dithiodiphosphonic Acids), and P(═S)—S—P(═S)(—R″)(—S—R″′); where R, R′, R″, derivatives thereof (S—S Bidentates, S—S and R″′ represent H, NH2 or any organic Tridentates, S—S Tetradentates) functional group wherein the number of carbon atoms ranges from 0 to 40, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #29: (RR′—N—)(R″—)P(═S)—S—S—P(═S)(—R″′)(—N— Dithioperoxydiphosphonamide, R″″R″″′), where R, R′, R″, R″′, R″″, and R″″′ Bis(dithioperoxyphosphonamide), and represent H, NH2 or any organic functional Poly(dithioperoxydiphosphonamide) (S—S group wherein the number of carbon atoms Bidentates, S—S Tridentates, S—S ranges from 0 to 40, optionally having halogen Tetradentates) or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #30: (R—O—)(R′—)P(═S)—S—S—P(═S)(—R″)(—O—R″′); or Dithioperoxydiphosphonic Acids, (R—S—)(R′—)P(═S)—S—S—P(═S)(—R″)(—S—R″′), Bis(dithioperoxyphosphonic Acids), where R, R′, R″, and R″′ represent H, NH2 or Poly(dithioperoxydiphosphonic Acids), and any organic functional group wherein the derivatives thereof (S—S Bidentates, S—S number of carbon atoms ranges from 0 to 40, Tridentates, S—S Tetradentates) optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #31: Dithiophosphonic (O═)PR(—S—R′)(—S—R″) or (S═)PR(—S—R′)(—O— Acids (Phosphonodithioic Acids), R″), where R, R′, and R″ represent H, NH2 or Bis(dithiophosphonic Acids), any organic functional group wherein the Poly(dithiophosphonic Acids), and number of carbon atoms ranges from 0 to 40, derivatives thereof (S—S Bidentates, S—S optionally having halogen or polarizing or Tridentates, S—S Tetradentates) water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #32: (S═)PR(—S—R′)(—S—R″), where R, R′, and R″ Trithiophosphonic Acids represent H, NH2 or any organic functional (Phosphonotrithioic Acids), group wherein the number of carbon atoms Bis(trithiophosphonic Acids), ranges from 0 to 40, optionally having halogen Poly(trithiophosphonic Acids), and or polarizing or water- derivatives thereof (S—S Bidentates, S—S insolubilizing/solubilizing groups attached. Tridentates, S—S Tetradentates) Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #33: (O═)PR(—S—S—R′)(—S—R″) or (S═)PR(—S—S—R′)(— Phosphono(dithioperoxo)thioic Acids), O—R″), where R, R′, and R″ represent H, NH2 or Bis[phosphono(dithioperoxo)thioic Acids], any organic functional group wherein the Poly[phosphono(dithioperoxo)thioic number of carbon atoms ranges from 0 to 40, Acids], and derivatives thereof (S—S optionally having halogen or polarizing or Bidentates, S—S Tridentates, S—S water-insolubilizing/solubilizing groups Tetradentates) attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #34: (S═)PR(—S—S—R′)(—S—R″), where R, R′, and R″ Phosphono(dithioperoxo)dithioic Acids), represent H, NH2 or any organic functional Bis[phosphono(dithioperoxo)dithioic group wherein the number of carbon atoms Acids], ranges from 0 to 40, optionally having halogen Poly[phosphono(dithioperoxo)dithioic or polarizing or water- Acids], and derivatives thereof (S—S insolubilizing/solubilizing groups attached. Bidentates, S—S Tridentates, S—S Ligand can also contain nonbinding N, O, S, or Tetradentates) P atoms. S Valence Stabilizer #35: R—S—R′CSOH or R—S—R′CSSH for S— S—(Alkylthio)thiocarboxylic Acids, S— (alkylthio)thiocarboxylic and S— (Arylthio)thiocarboxylic Acids, and S,S— (arylthio)thiocarboxylic acids, and HSOCR—S— thiobisthiocarboxylic Acids (S—S Bidentates R′COSH or HSSCR—S—R′CSSH for S,S— and S—S Tridentates) thiobisthiocarboxylic acids, where R and R′ represent H or any organic functional group wherein the number of carbon atoms ranges from 0 to 40, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #36: R—S—S—R′CSOH or R—S—S—R′CSSH for S— S—(Alkyldisulfido)thiocarboxylic Acids, S— (alkyldisulfido)thiocarboxylic and S— (Aryldisulfido)thiocarboxylic Acids, and (aryldisulfido)thiocarboxylic acids, and S,S′—Disulfidobisthiocarboxylic Acids (S—S HSOCR—S—S—R′COSH or HSSCR—S—S—R′CSSH Bidentates and S—S Tridentates) for S,S′—disulfidobisthiocarboxylic acids, where R and R′ represent H or any organic functional group wherein the number of carbon atoms ranges from 0 to 40, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #37: R—CH(—SR″)—CH(—SR″′)—R′, and R—C(— 1,2-Dithiolates, Bis(1,2-dithiolates), and SR″)═C(—SR″′)—R′, where R, R′, R″, and R″′ Poly(1,2-dithiolates) (S—S Bidentates, S—S represent H, NH2 or any organic functional Tridentates, S—S Tetradentates) group wherein the number of carbon atoms ranges from 0 to 40, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #38: RN—C(═O)—CHR′—S—C(═S) for rhodanines, and Rhodanines and Bis(rhodanines) (S—S R—[N—C(═O)—CHR′—S—C(═S)]2 for Bidentates and S—S Tetradentates) bis(rhodanines), where R and R′ represent H, NH2 or any organic functional group wherein the number of carbon atoms ranges from 0 to 40, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #39: RN═C(SH)(SH), where R represents H, NH2 or Dithiocarbimates, Bis(dithiocarbimates), any organic functional group wherein the and Poly(dithiocarbimates) (S—S Bidentates, number of carbon atoms ranges from 0 to 40, S—S Tridentates, and S—S Tetradentates) optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #40: RS+═C(SH)(SH) or RS—C(═S)(SH), where R Thioxanthates, Bis(thioxanthates), and represents H, NH2 or any organic functional Poly(thioxanthates) (S—S Bidentates and S—S group wherein the number of carbon atoms Tetradentates) ranges from 0 to 40, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #41: RO+═C(SH)(SH) or RO—C(═S)(SH), where R Xanthates, Bis(xanthates), and represents H, NH2 or any organic functional Poly(xanthates) (S—S Bidentates and S—S group wherein the number of carbon atoms Tetradentates) ranges from 0 to 40, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #42: Typically RR′R″P═C(SH)(SH) [pentavalent P], Phosphinodithioformates (S—S Bidentates) although RR′P—C(═S)(SH) [trivalent P] may be acceptable in some situations, where R, R′, and R″ represent H, NH2 or any organic functional group wherein the number of carbon atoms ranges from 0 to 40, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #43: R—S—C(—S—R″)—O—R′ for dithioborates, R—S—C(—S— Alkyl- and Aryl- Dithioborates, R″)—S—R′ for trithioborates, and R—S—S—C(—S— Trithioborates, Perthioborates, R″)—S—R′ for perthioborates, where R, R′, and Bis(dithioborates), Bis(trithioborates), and R″ represent H, NH2 or any organic functional Bis(perthioborates) (S—S Bidentates and S—S group wherein the number of carbon atoms Tetradentates) ranges from 0 to 40, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #44: R—C(—S—R″)—S—R′, where R, R′, and R″ Alkyl- and Aryl- Dithioboronates, and represent H, NH2 or any organic functional Bis(dithioboronates) (S—S Bidentates and S—S group wherein the number of carbon atoms Tetradentates) ranges from 0 to 40, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #45: (O═)As(—S—R)(—S—R′)(—S—R″) or (S═)As(—S—R)(— Trithioarsonic Acids (Arsonotrithioic S—R′)(—O—R″) for trithioarsonic acid; (O═)As(— Acids), Dithioarsonic Acids O—R)(—S—R′)(—S—R″) or (S═)As(—S—R)(—O—R′)(— (Arsonodithioic Acids), Tetrathioarsonic O—R″) for dithioarsonic acid, or (S═)As(—S—R)(— Acids (Arsonotetrathioic Acids), and S—R′)(—S—R″) for tetrathioarsonic acid, where R, derivatives thereof (S—S Bidentates, S—S R′, and R″ represent H, NH2 or any organic Tridentates, S—S Tetradentates) functional group wherein the number of carbon atoms ranges from 0 to 40, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #46: (O═)Sb(—S—R)(—S—R′)(—S—R″) or (S═)Sb(—S—R)(— Trithioantimonic Acids (Stibonotrithioic S—R′)(—O—R″) for trithioantimonic acid; Acids), Dithioantimonic Acids (O═)Sb(—O—R)(—S—R′)(—S—R″) or (S═)Sb(—S—R)(— (Stibonodithioic Acids), Tetrathioantimonic O—R′)(—O—R″) for dithioantimonic acid, or Acids (Stibonotetrathioic Acids), and (S═)Sb(—S—R)(—S—R′)(—S—R″) for derivatives thereof (S—S Bidentates, S—S tetrathioantimonic acid, where R, R′, and R″ Tridentates, S—S Tetradentates) represent H, NH2 or any organic functional group wherein the number of carbon atoms ranges from 0 to 40, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #47: RR′R″P═S for phosphine P—sulfides, and Phosphine P—sulfides and Amino- (RR′N)(R″R″′N)(R″″R″″′N)P═S for amino— substituted Phosphine sulfides (S substituted phosphine sulfides, where R, R′, R″, Monodentates) R″′, R″″, and R″″′ represent H, Cl, Br, NH2 or any organic functional group wherein the number of carbon atoms ranges from 0 to 40, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. (Rs are typically aromatic or heterocyclic for phosphine P-sulfides.) Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #48: RR′R″As═S for arsine As-sulfides, and Arsine As-sulfides and Amino-substituted (RR′N)(R″R″′N)(R″″R″″′N)As═S for amino- Arsine sulfides (S Monodentates) substituted arsine sulfides, where R, R′, R″, R″′, R″″, and R″″′ represent H, Cl, Br, NH2 or any organic functional group wherein the number of carbon atoms ranges from 0 to 40, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. (Rs are typically aromatic or heterocyclic for arsine As-sulfides.) Ligand can also contain nonbinding N, O, S, or P atoms. S Valence Stabilizer #49: Thiols (HS—R, HS—R—SH, etc.), where R and R′ Thiolates (S Monodentates) represent H or any organic functional group wherein the number of carbon atoms ranges from 0 to 35, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. S Valence Stabilizer #50: Sulfide (—S2−) ligands bound directly to the high Sulfide ligands (S Monodentates) valence metal ion. P Valence Stabilizer #1: PH3, PH2R, PHR2, and PR3 where R represents Monophosphines (P Monodentates) H or any organic functional group wherein the wherein at least one Phosphorus Atom is a number of carbon atoms ranges from 0 to 35, Binding Site optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, P, As, O, S, or Se atoms. P Valence Stabilizer #2: R′—P—R—P—R″, where R, R′, and R″ represent H Diphosphines (a P—P Bidentate) wherein at or any organic functional group wherein the least one Phosphorus Atom is a Binding number of carbon atoms ranges from 0 to 35, Site optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, P, As, O, S, or Se atoms. P Valence Stabilizer #3: R—P—R′—P—R″—P—R″′, where R, R′, R″, and R″′ Triphosphines (either P—P Bidentates or P- represent H or any organic functional group P—P Tridentates) wherein at least one wherein the number of carbon atoms ranges Phosphorus Atom is a Binding Site from 0 to 35, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, P, As, O, S, or Se atoms. P Valence Stabilizer #4: R—P—R′—P—R″—P—R″′—P—R″″, where R, R′, R″, Tetraphosphines (P—P Bidentates, P—P R″′, and R″″ represent H or any organic Tridentates, or P—P Tetradentates) wherein functional group wherein the number of carbon at least one Phosphorus Atom is a Binding atoms ranges from 0 to 35, optionally having Site halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, P, As, O, S, or Se atoms. P Valence Stabilizer #5: R—P—R′—P—R″—P—R″′—P—R″″—P—R″″′, where R, R′, Pentaphosphines (P—P Bidentates, P—P R″, R″′, R″″, and R″″′ represent H or any Tridentates, or P—P Tetradentates) wherein organic functional group wherein the number of at least one Phosphorus Atom is a Binding carbon atoms ranges from 0 to 35, optionally Site having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, P, As, O, S, or Se atoms. P Valence Stabilizer #6: R—P—R′—P—R″—P—R″′—P—R″″—P—R″″′—P—R″″″, Hexaphosphines (P—P Bidentates, P—P where R, R′, R″, R″′, R″″, R″″′, and R″″″ Tridentates, P—P Tetradentates, or P—P represent H or any organic functional group Hexadentates) wherein at least one wherein the number of carbon atoms ranges Phosphorus Atom is a Binding Site from 0 to 35, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, P, As, O, S, or Se atoms. P Valence Stabilizer #7: Five membered heterocyclic ring containing Five-Membered Heterocyclic Rings one, two, or three phosphorus atoms, all of containing One, Two, or Three Phosphorus which may or may not function as binding sites. Atoms wherein at least one Phosphorus Can include other ring systems bound to this Atom is a Binding Site (P Monodentates or heterocyclic ring, but they do not coordinate P—P Bidentates) with the stabilized, high valence metal ion. Ring can also contain O, S, N, As, or Se atoms. This 5-membered ring and/or attached, uncoordinating rings may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. P Valence Stabilizer #8: Six membered heterocyclic ring containing one, Six-Membered Heterocyclic Rings two, or three phosphorus atoms, all of which containing One, Two, or Three Phosphorus may or may not function as binding sites. Can Atoms wherein at least one Phosphorus include other ring systems bound to this Atom is a Binding Site (P Monodentates or heterocyclic ring, but they do not coordinate P—P Bidentates) with the stabilized, high valence metal ion. Ring can also contain O, S, N, As, or Se atoms. This 6-membered ring and/or attached, uncoordinating rings may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. P Valence Stabilizer #9: Five membered heterocyclic ring(s) containing Five-Membered Heterocyclic Rings one, two, or three phosphorus atoms. In containing One, Two, or Three Phosphorus addition, ligand contains additional phosphorus- Atoms at least one additional Phosphorus containing substituents (usually phosphines) Atom Binding Site not in a Ring (P that constitute P binding sites. Can include Monodentates, P—P Bidentates, P—P other ring systems bound to the heterocyclic Tridentates, P—P Tetradentates, or P—P ring or to the P-containing substituent, but they Hexadentates) do not coordinate with the stabilized, high valence metal ion. Ring(s) can also contain O, N, S, As or Se atoms. This 5-membered ring(s) and/or attached, uncoordinating rings and/or P- containing substituent(s) may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. P Valence Stabilizer #10: Six membered heterocyclic ring(s) containing Six-Membered Heterocyclic Rings one, two, or three phosphorus atoms. In containing One, Two, or Three Phosphorus addition, ligand contains additional phosphorus- Atoms at least one additional Phosphorus containing substituents (usually phosphines) Atom Binding Site not in a Ring (P that constitute P binding sites. Can include Monodentates, P—P Bidentates, P—P other ring systems bound to the heterocyclic Tridentates, P—P Tetradentates, or P—P ring or to the P-containing substituent, but they Hexadentates) do not coordinate with the stabilized, high valence metal ion. Ring(s) can also contain O, N, S, As or Se atoms. This 6-membered ring(s) and/or attached, uncoordinating rings and/or P- containing substituent(s) may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. P Valence Stabilizer #11: Five membered heterocyclic ring(s) containing Five-Membered Heterocyclic Rings one, two, or three phosphorus atoms. In containing One, Two, or Three Phosphorus addition, ligand contains additional phosphorus- Atoms at least one additional Phosphorus containing rings that constitute P binding sites. Atom Binding Site in a separate Ring (P Can include other ring systems bound to the P- Monodentates, P—P Bidentates, P—P containing heterocyclic rings, but they do not Tridentates, P—P Tetradentates, or P—P coordinate with the stabilized, high valence Hexadentates) metal ion. Ring(s) can also contain O, N, S, As, or Se atoms. This 5-membered ring(s) and/or additional P-containing ring(s) and/or attached, uncoordinating rings may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. P Valence Stabilizer #12: Six membered heterocyclic ring(s) containing Six-Membered Heterocyclic Rings one, two, or three phosphorus atoms. In containing One, Two, or Three Phosphorus addition, ligand contains additional phosphorus- Atoms at least one additional Phosphorus containing rings that constitute P binding sites. Atom Binding Site in a separate Ring (P Can include other ring systems bound to the P- Monodentates, P—P Bidentates, P—P containing heterocyclic rings, but they do not Tridentates, P—P Tetradentates, or P—P coordinate with the stabilized, high valence Hexadentates) metal ion. Ring(s) can also contain O, N, S, As, or Se atoms. This 6-membered ring(s) and/or additional P-containing ring(s) and/or attached, uncoordinating rings may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. P Valence Stabilizer #13: Macrocyclic ligands containing two, three, four, two-, Three-, Four-, Five-, Six-, and Eight- five, six, or eight phosphorus binding sites to Membered Macrocyclics, Macrobicyclics, valence stabilize the central metal ion. Can and Macropolycyclics (including include other hydrocarbon or ring systems Catapinands, Cryptands, Cyclidenes, and bound to this macrocyclic ligand, but they do Sepulchrates) wherein all Binding Sites are not coordinate with the stabilized, high valence composed of Phosphorus and are not metal ion. This ligand and/or attached, contained in Component Heterocyclic uncoordinating hydrocarbons/rings may or may Rings (P—P Bidentates, P—P Tridentates, P—P not have halogen or polarizing or water- Tetradentates, and P—P Hexadentates) insolubilizing/solubilizing groups attached. P Valence Stabilizer #14: Macrocyclic ligands containing a total of four, Four-, six-, or Eight-Membered six, or eight five-membered heterocyclic rings Macrocyclics, Macrobicyclics, and containing phosphorus binding sites. Can Macropolycyclics (including Catapinands, include other hydrocarbon/ring systems bound Cryptands, Cyclidenes, and Sepulchrates) to this macrocyclic ligand, but they do not wherein all Binding Sites are composed of coordinate with the stabilized, high valence Phosphorus and are contained in metal ion. This ligand and/or attached, Component 5-Membered Heterocyclic uncoordinating hydrocarbon/rings may or may Rings (P—P Tridentates, P—P Tetradentates, not have halogen or polarizing or water- or P—P Hexadentates) insolubilizing groups attached. P Valence Stabilizer #15: Macrocyclic ligands containing at least one 5- Four-, six-, or Eight-Membered membered heterocyclic ring. These Macrocyclics, Macrobicyclics, and heterocyclic rings provide phosphorus binding Macropolycyclics (including Catapinands, sites to valence stabilize the central metal ion. Cryptands, Cyclidenes, and Sepulchrates) Other phosphine binding sites can also be wherein all Binding Sites are composed of included in the macrocyclic ligand, so long as Phosphorus and are contained in a the total number of binding sites is four, six, or Combination of 5-Membered Heterocyclic eight. Can include other hydrocarbon/ring Rings and Phosphine Groups (P—P systems bound to this macrocyclic ligand, but Tridentates, P—P Tetradentates, or P—P they do not coordinate with the stabilized, high Hexadentates) valence metal ion. This ligand and/or attached, uncoordinating hydrocarbon/rings may or may not have halogen or polarizing or water- insolubilizing groups attached. P Valence Stabilizer #16: Macrocyclic ligands containing a total of four, Four-, six-, or Eight-Membered six, or eight six-membered heterocyclic rings Macrocyclics, Macrobicyclics, and containing phosphorus binding sites. Can Macropolycyclics (including Catapinands, include other hydrocarbon/ring systems bound Cryptands, Cyclidenes, and Sepulchrates) to this macrocyclic ligand, but they do not wherein all Binding Sites are composed of coordinate with the stabilized, high valence Phosphorus and are contained in metal ion. This ligand and/or attached, Component 6-Membered Heterocyclic uncoordinating hydrocarbon/rings may or may Rings (P—P Tridentates, P—P Tetradentates, not have halogen or polarizing or water- or P—P Hexadentates) insolubilizing groups attached. P Valence Stabilizer #17: Macrocyclic ligands containing at least one 6- Four-, six-, or Eight-Membered membered heterocyclic ring. These Macrocyclics, Macrobicyclics, and heterocyclic rings provide phosphorus binding Macropolycyclics (including Catapinands, sites to valence stabilize the central metal ion. Cryptands, Cyclidenes, and Sepulchrates) Other phosphine binding sites can also be wherein all Binding Sites are composed of included in the macrocyclic ligand, so long as Phosphorus and are contained in a the total number of binding sites is four, six, or Combination of 6-Membered Heterocyclic eight. Can include other hydrocarbon/ring Rings and Phosphine Groups (P—P systems bound to this macrocyclic ligand, but Tridentates, P—P Tetradentates, or P—P they do not coordinate with the stabilized, high Hexadentates) valence metal ion. This ligand and/or attached, uncoordinating hydrocarbon/rings may or may not have halogen or polarizing or water- insolubilizing groups attached. O Valence Stabilizer #1: R—O—C(═O)—S—S—C(═O)—O—R′, where R and R′ Dithioperoxydicarbonic Acids, represent H, NH2 or any organic functional Bis(dithioperoxydicarbonic acids), group wherein the number of carbon atoms poly(dithioperoxydicarbonic acids), and ranges from 0 to 40, optionally having halogen derivatives thereof (O—O Bidentates, O—O or polarizing or water- Tridentates, O—O Tetradentates) insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #2: (R—O—)(R′—)P(═O)—NH—P(═O)(—R″)(—O—R″′) for Imidodiphosphonic Acids, imidodiphosphonic acids, and (R—O—)(R′—) Hydrazidodiphosphonic Acids, P(═O)—NH—NH—P(═O)(—R″)(—O—R″′) for Bis(imidodiphosphonic Acids), hydrazidodiphosphonic acids; where R, R′, R″, Bis(hydrazidodiphosphonic Acids), and R″′ represent H, NH2 or any organic Poly(imidodiphosphonic Acids), functional group wherein the number of carbon Poly(hydrazidodiphosphonic Acids), and atoms ranges from 0 to 40, optionally having derivatives thereof (O—O Bidentates, O—O halogen or polarizing or water- Tridentates, O—O Tetradentates) insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #3: (RR′—N—)(R″—)P(═O)—NH—P(═O)(—R″′)(—N— Imidodiphosphonamides, R″″R″″′) for imidodiphosphonamides, and — Hydrazidodiphosphonamides, NH—NH—derivatives for Bis(imidodiphosphonamides), hydrazidodiphosphonamides, where R, R′, R″, Bis(hydrazidodiphosphonamides), R″′, R″″, and R″″′ represent H, NH2 or any Poly(imidodiphosphonamides), and organic functional group wherein the number of Poly(hydrazidodiphosphonamides) (O—O carbon atoms ranges from 0 to 40, optionally Bidentates, O—O Tridentates, O—O having halogen or polarizing or water- Tetradentates) insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #4: (RR′—N—)(R″—)P(═O)—O—P(═O)(—R″′)(—N— Diphosphonamides, R″″R″″′), where R, R′, R″, R″′, R″″, and R″″′ Bis(diphosphonamides), and represent H, NH2 or any organic functional Poly(diphosphonamides) (O—O Bidentates, group wherein the number of carbon atoms O—O Tridentates, O—O Tetradentates) ranges from 0 to 40, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #5: R—O—C(═O)—O—R′, where R, and R′ represent H, Carbonates and Bis(carbonates) (O—O NH2 or any organic functional group wherein Bidentates and O—O Tetradentates) the number of carbon atoms ranges from 0 to 40, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #6: RR′N—NR″—C(═O)(OH), where R and R′ Carbazates (carbazides), Bis(carbazates), represent H, NH2 or any organic functional and Poly(carbazates) (O—O Bidentates, O—O group wherein the number of carbon atoms Tridentates, and O—O Tetradentates; or ranges from 0 to 40, optionally having halogen possibly N—O Bidentates, N—O Tridentates, or polarizing or water- and N—O Tetradentates) insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #7: (O═)As(—O—R)(—O—R′)(—O—R″), where R, R′, and Arsonic Acids, Bis(arsonic acids), R″ represent H, NH2 or any organic functional Poly(arsonic acids), and derivatives thereof group wherein the number of carbon atoms (O—O Bidentates, O—O Tridentates, O—O ranges from 0 to 40, optionally having halogen Tetradentates) or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #8: R—O—C(—O—R″)—O—R′, where R, R′, and R″ Alkyl- and Aryl- Borates and Bis(borates) represent H, NH2 or any organic functional (O—O Bidentates and O—O Tetradentates) group wherein the number of carbon atoms ranges from 0 to 40, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #9: R—C(—O—R″)—O—R′, where R, R′, and R″ Alkyl- and Aryl- Boronates and represent H, NH2 or any organic functional Bis(boronates) (O—O Bidentates and O—O group wherein the number of carbon atoms Tetradentates) ranges from 0 to 40, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #10: RR′R″P═O for phosphine P-oxides, and Phosphine P-oxides and Amino-substituted (RR′N)(R″R″′N)(R″″R″″′N)P═O for amino- Phosphine oxides (O Monodentates) substituted phosphine oxides, where R, R′, R″, R″′,R″″, and R″″′, represent H, Cl, Br, NH2 or any organic functional group wherein the number of carbon atoms ranges from 0 to 40, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. (Rs are typically aromatic or heterocyclic for phosphine P-oxides.) Ligand can also contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #11: RR′R″As═O for arsine As-oxides, and Arsine As-oxides and Amino-substituted (RR′N)(R″R″′N)(R″″R″″′N)As═O for amino- Arsine oxides (O Monodentates) substituted arsine oxides, where R, R′, R″, R″′, R″″, and R″″′ represent H, Cl, Br, NH2 or any organic functional group wherein the number of carbon atoms ranges from 0 to 40, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. (Rs are typically aromatic or heterocyclic for arsine As-oxides.) Ligand can also contain nonbinding N, O, S, or P atoms. O Valence Stabilizer #12: Five membered heterocyclic ring containing one Five-Membered Heterocyclic Rings or two oxygen atoms, both of which may or containing One or Two Oxygen Atoms may not function as binding sites. Can include wherein at least one Oxygen Atom is a other ring systems bound to this heterocyclic Binding Site (O Monodentates or O—O ring, but they do not coordinate with the Bidentates) stabilized, high valence metal ion. Ring can also contain O, S, or P atoms. This 5-membered ring and/or attached, uncoordinating rings may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. O Valence Stabilizer #13: Six membered heterocyclic ring containing one Six-Membered Heterocyclic Rings or two oxygen atoms, both of which may or containing One or Two Oxygen Atoms may not function as binding sites. Can include wherein at least one Oxygen Atom is a other ring systems bound to this heterocyclic Binding Site (O Monodentates or O—O ring, but they do not coordinate with the Bidentates) stabilized, high valence metal ion. Ring can also contain O, S, or P atoms. This 6-membered ring and/or attached, uncoordinating rings may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. O Valence Stabilizer #14: Five membered heterocyclic ring(s) containing Five-Membered Heterocyclic Rings one or two oxygen atoms. In addition, ligand containing One or Two Oxygen Atoms and contains additional oxygen-containing having at least one additional Oxygen Atom substituents (usually hydroxyl or ester groups) Binding Site not in a Ring (O that constitute O binding sites. Can include Monodentates, O—O Bidentates, O other ring systems bound to the heterocyclic Tridentates, O Tetradentates, or O ring or to the O-containing substituent, but they Hexadentates) do not coordinate with the stabilized, high valence metal ion. Ring(s) can also contain O, S, or P atoms. This 5-membered ring(s) and/or attached, uncoordinating rings and/or O- containing substituent(s) may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. O Valence Stabilizer #15: Six membered heterocyclic ring(s) containing Six-Membered Heterocyclic Rings one or two oxygen atoms. In addition, ligand containing One or Two Oxygen Atoms and contains additional oxygen-containing having at least one additional Oxygen Atom substituents (usually hydroxyl or ester groups) Binding Site not in a Ring (O that constitute O binding sites. Can include Monodentates, O—O Bidentates, O other ring systems bound to the heterocyclic Tridentates, O Tetradentates, or O ring or to the O-containing substituent, but they Hexadentates) do not coordinate with the stabilized, high valence metal ion. Ring(s) can also contain O, S, or P atoms. This 6-membered ring(s) and/or attached, uncoordinating rings and/or O- containing substituent(s) may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. O Valence Stabilizer #16: Five membered heterocyclic ring(s) containing Five-Membered Heterocyclic Rings one or two oxygen atoms. In addition, ligand containing One or Two Oxygen Atoms and contains additional oxygen-containing rings that having at least one additional Oxygen Atom constitute O binding sites. Can include other Binding Site in a Separate Ring (O ring systems bound to the O-containing Monodentates, O—O Bidentates, O heterocyclic rings, but they do not coordinate Tridentates, O Tetradentates, or O with the stabilized, high valence metal ion. Hexadentates) Ring(s) can also contain O, S, or P atoms. This 5-membered ring(s) and/or additional O- containing ring(s) and/or attached, uncoordinating rings may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. O Valence Stabilizer #17: Six membered heterocyclic ring(s) containing Six-Membered Heterocyclic Rings one or two oxygen atoms. In addition, ligand containing One or Two Oxygen Atoms and contains additional oxygen-containing rings that having at least one additional Oxygen Atom constitute O binding sites. Can include other Binding Site in a Separate Ring (O ring systems bound to the O-containing Monodentates, O—O Bidentates, O heterocyclic rings, but they do not coordinate Tridentates, O Tetradentates, or O with the stabilized, high valence metal ion. Hexadentates) Ring(s) can also contain O, S, or P atoms. This 6-membered ring(s) and/or additional O- containing ring(s) and/or attached, uncoordinating rings may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. O Valence Stabilizer #18: Macrocyclic ligands containing four, five, six, Four-, Five-, Six-, Seven-, Eight-, and Ten- seven, eight, or ten oxygen binding sites to Membered Macrocyclics, Macrobicyclics, valence stabilize the central metal ion. Can and Macropolycyclics (including include other hydrocarbon or ring systems Catapinands, Cryptands, Cyclidenes, and bound to this macrocyclic ligand, but they do Sepulchrates) wherein all Binding Sites are not coordinate with the stabilized, high valence composed of Oxygen (usually ester or metal ion. This ligand and/or attached, hydroxyl groups) and are not contained in uncoordinating hydrocarbons/rings may or may Component Heterocyclic Rings (O—O not have halogen or polarizing or water- Bidentates, O—O Tridentates, O—O insolubilizing/solubilizing groups attached. Tetradentates, and O—O Hexadentates) O Valence Stabilizer #19: Macrocyclic ligands containing a total of four, Four-, Five-, Six-, Seven-, Eight-, and Ten- five, six, seven, eight, or ten five-membered Membered Macrocyclics, Macrobicyclics, heterocyclic rings containing oxygen binding and Macropolycyclics (including sites. Can include other hydrocarbon or ring Catapinands, Cryptands, Cyclidenes, and systems bound to this macrocyclic ligand, but Sepulchrates) wherein all Binding Sites are they do not coordinate with the stabilized, high composed of Oxygen and are contained in valence metal ion. This ligand and/or attached, Component 5-Membered Heterocyclic uncoordinating hydrocarbons/rings may or may Rings (O—O Bidentates, O—O Tridentates, not have halogen or polarizing or water- O—O Tetradentates, and O—O Hexadentates) insolubilizing/solubilizing groups attached. O Valence Stabilizer #20: Macrocyclic ligands containing a total of four, Four-, Five-, Six-, Seven-, Eight-, and Ten- five, six, seven, eight, or ten six-membered Membered Macrocyclics, Macrobicyclics, heterocyclic rings containing oxygen binding and Macropolycyclics (including sites. Can include other hydrocarbon or ring Catapinands, Cryptands, Cyclidenes, and systems bound to this macrocyclic ligand, but Sepulchrates) wherein all Binding Sites are they do not coordinate with the stabilized, high composed of Oxygen and are contained in valence metal ion. This ligand and/or attached, Component 6-Membered Heterocyclic uncoordinating hydrocarbons/rings may or may Rings (O—O Bidentates, O—O Tridentates, not have halogen or polarizing or water- O—O Tetradentates, and O—O Hexadentates) insolubilizing/solubilizing groups attached. N—S Valence Stabilizer #1: RC(═NH)SR′, where R and R′ represent H or Thioimidates, Dithioimidates, any organic functional group wherein the Polythioimidates, and Derivatives of number of carbon atoms ranges from 0 to 40, Thioimidic Acid (N—S Bidentates and N—S optionally having halogen or polarizing or Tetradentates) water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—S Valence Stabilizer #2: RR′—N—C(═NH)—NR″—CS—NR″′R″″ for Thioguanylureas, Guanidinothioureas, thioguanylureas, and RR′—N—C(═NH)—NR″—NH— Bis(thioguanylureas), CS—NR″′R″″ for guanidinothioureas, where R, Bis(guanidinothioureas), R′, R″, R″′, and R″″ represent H, NH2, or any Poly(thioguanylureas), and organic functional group wherein the number of Poly(guanidinothioureas) (N—S Bidentates carbon atoms ranges from 0 to 40, optionally and N—S Tetradentates) having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—S Valence Stabilizer #3: RR′—N—C(═NH)—NR″—CS—R″′ for N— Amidinothioamides, Guanidinothioamides, amidinothioamides, or RR′—N—C(═NH)— Bis(amidinothioamides), CR″R″′—CS—N—R″″R″″′ for 2— Bis(guanidinothioamides), amidinothioacetamides, and RR′—N—C(═NH)— Poly(amidinothioamides), and NR″—NH—CS—R″′ for guanidinothioamides, Poly(guanidinothioamides) (including both where R, R′, R″, R″′, R″″, and R″″′ represent N-amidinothioamides and 2- H, NH2 , or any organic functional group amidinothioacetamides) (N—S Bidentates wherein the number of carbon atoms ranges and N—S Tetradentates) from 0 to 40, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—S Valence Stabilizer #4: R—C(═NH)—NR′—CS—R″, where R, R′, and R″, Imidoylthioamides, represent H or any organic functional group Bis(imidoylthioamides), and wherein the number of carbon atoms ranges Poly(imidoylthioamides) (N—S Bidentates from 0 to 40, optionally having halogen or and N—S Tetradentates) polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—S Valence Stabilizer #5: RR′NCSNR″R″′, where R, R′, R″, and R″′ Thioureas, Bis(thioureas), and represent H, NH2, or any organic functional Poly(thioureas), including Thiourylene group wherein the number of carbon atoms Complexes (N—S Bidentates, N—S ranges from 0 to 40, optionally having halogen Tridentates, and N—S Tetradentates) or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—S Valence Stabilizer #6: RCSNR′R″, where R, R′, and R″ represent H, Thiocarboxamides, Bis(thiocarboxamides), NH2, or any organic functional group wherein and Poly(thiocarboxamides) (N—S the number of carbon atoms ranges from 0 to Bidentates, N—S Tridentates, and N—S 40, optionally having halogen or polarizing or Tetradentates) water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—S Valence Stabilizer #7: RR′—N—S(═NH)—N—R″R″′, where R, R′, R″, and Imidosulfurous Diamides and R″′ represent H or any organic functional group Bis(imidosulfurous diamides) (N—S wherein the number of carbon atoms ranges Bidentates, N—S Tridentates, and N—S from 0 to 40, optionally having halogen or Tetradentates) polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—S Valence Stabilizer #8: R—N═S═N—R′, where R and R′ represent H or Sulfurdiimines, Bis(sulfurdiimines), and any organic functional group wherein the Poly(sulfurdiimines) (N—S Bidentates, N—S number of carbon atoms ranges from 0 to 40, Tridentates, and N—S Tetradentates) optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—S Valence Stabilizer #9: (NH═)PR(OR′)(SR″) for phosphonimidothioic Phosphonimidothioic Acid, acid and (NH═)PR(SR′)(SR″) for Phosphonimidodithioic Acid, phosphonimidodithioic acid, where R, R′, and Bis(Phosphonimidothioic acid); R″ represent H or any organic functional group Bis(Phosphonimidodithioic acid), and wherein the number of carbon atoms ranges derivatives thereof (N—S Bidentates, N—S from 0 to 40, optionally having halogen or Tetradentates) polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—S Valence Stabilizer #10: (S═)PR(—NR′R″)(—NR″′R″″), where R, R′, R″, Phosphonothioic Diamides, R″′, and R″″ represent H or any organic Bis(phosphonothioic diamides), and functional group wherein the number of carbon Poly(phosphonothioic diamides) (N—S atoms ranges from 0 to 40, optionally having Bidentates and N—S Tetradentates) halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—S Valence Stabilizer #11: (S═)PR(—NR′R″)(—OR″′) or (O═)PR(—NR′R″)(— Phosphonamidothioic Acid, SR″′) for phosphonamidothioic acid, (S═)PR(— Phosphonamidimidodithioic Acid, NR′R″)(—SR″′) for phosphonamidimidodithioic Bis(phosphonamidothioic acid), acid, where R, R′, R″, and R″′ represent H or Bis(phosphonamidimidodithioic acid), any organic functional group wherein the poly(phosphonamidothioic acid), and number of carbon atoms ranges from 0 to 40, poly(phosphonamidimidodithioic acid), and optionally having halogen or polarizing or derivatives thereof (N—S Bidentates and N—S water-insolubilizing/solubilizing groups Tetradentates) attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—S Valence Stabilizer #12: R—C(═S)—CR′═CR″—NHR″′, where R, R′, R″, Beta-Aminothiones (N-Substituted 3- and R″′ represent H, or any organic functional amino-2-propenethioaldehydes), Bis(beta- group wherein the number of carbon atoms aminothiones), and Poly(beta- ranges from 0 to 40, optionally having halogen aminothiones) (N—S Bidentates and N—S or polarizing or water- Tetradentates) insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—S Valence Stabilizer #13: RR′—N—C(═S)—CR″═C(—NHR″′)R″″ for 3- 3-Aminothioacrylamides (3-Amino-2- aminothioacrylamides, and RR′—N—C(═S)— thiopropenamides), 3,3- CR″═C(—NHR″′)(—NR″″R″″′) for 3,3- Diaminothioacrylamides, Bis(3- diaminothioacrylamides, where R, R′, R″, R″′, aminothioacrylamides), Bis(3,3- R″″, R″″′ represent H, NH2, or any organic diaminoacrylamides), Poly(3- functional group wherein the number of carbon aminothioacrylamides), and Poly(3,3- atoms ranges from 0 to 40, optionally having diaminothioacrylamides) (N—S Bidentates halogen or polarizing or water- and N—S Tetradentates) insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—S Valence Stabilizer #14: R—O—C(═S)—CR′═C(—NHR″)R″′ or R—S—C(═S)— 3-Aminothioacrylic Acids (3-Amino-2- CR′═C(—NHR″)R″′ for 3-aminothioacrylic thiopropenoic acids), 3-Mercapto-3- acids, and R—O—C(═S)—CR′═C(—NHR″)(—S—R″′) aminothioacrylic acids, Bis(3- or R—S—C(═S)—CR′═C(—NHR″)(—S—R″′) for 3- aminothioacrylic acids), Bis(3-Hydroxy-3- mercapto-3-aminothioacrylic acids, where R, aminothioacrylic acids), Poly(3- R′, R″, and R″′ represent H, NH2, or any aminothioacrylic acids), and Poly(3- organic functional group wherein the number of Hydroxy-3-aminothioacrylic acids), and carbon atoms ranges from 0 to 40, optionally derivatives thereof (N—S Bidentates and N—S having halogen or polarizing or water- Tetradentates) insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—S Valence Stabilizer #15: R—C(═S)—N═CHR′, where R′ represents an N-Thioacyl Benzylidenimines, Bis(N- aromatic derivative (i.e. —C6H5), and R represent thioacyl benzylidenimines), and Poly(N- H, NH2, or any organic functional group thioacyl benzylidenimines) (N—S Bidentates wherein the number of carbon atoms ranges and N—S Tetradentates) from 0 to 40, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—S Valence Stabilizer #16: R—C(═S)—C(═NOH)—R′, where R and R′ Thiocarbonyl oximes, Bis(thiocarbonyl represent H, NH2, or any organic functional oximes), and Poly(thiocarbonyl oximes) group wherein the number of carbon atoms (N—S Bidentates, N—S Tridentates, and N—S ranges from 0 to 40, optionally having halogen Tetradentates) or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—S Valence Stabilizer #17: R—CH(—SH)—C(═NOH)—R′, where R, R′, and R″ Mercapto oximes, Bis(mercapto oximes), represent H, NH2, or any organic functional and Poly(mercapto oximes) (including 2- group wherein the number of carbon atoms sulfur heterocyclic oximes) (N—S ranges from 0 to 40, optionally having halogen Bidentates, N—S Tridentates, N—S or polarizing or water- Tetradentates, and N—S Hexadentates) insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—S Valence Stabilizer #18: o—(O2N—)(HS—)Ar, where Ar represents an 2-Nitrothiophenols (2-nitrobenzenethiols) aromatic group or heterocyclic wherein the (N—S Bidentates) number of carbon atoms ranges from 6 to 40, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—S Valence Stabilizer #19: o—(NC—(CH2)0-1)(HS—)Ar, where Ar represents 2-Nitrilothiophenols (N—S Bidentates) an aromatic group or heterocyclic wherein the number of carbon atoms ranges from 6 to 40, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—S Valence Stabilizer #20: R—C(═S)—NHNR′R″, where R, R′, and R″ Thiohydrazides, Bis(thiohydrazides), and represent H or any organic functional group Poly(thiohydrazides) (N—S Bidentates and wherein the number of carbon atoms ranges N—S Tetradentates) from 0 to 40, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—S Valence Stabilizer #21: RR′—N—C(═S)—NHNR″R″′, where R, R′, and R″ Thiosemicarbazides, represent H or any organic functional group Bis(thiosemicarbazides), and wherein the number of carbon atoms ranges Poly(thiosemicarbazides) (N—S Bidentates, from 0 to 40, optionally having halogen or N—S Tetradentates, and N—S Hexadentates) polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—S Valence Stabilizer #22: Macrocyclic ligands containing five, seven, or Five-, Seven-, or Nine-Membered nine binding sites composed of nitrogen and Macrocyclics, Macrobicyclics, and sulfur to valence stabilize the central metal ion. Macropolycyclics (including Catapinands, Can include other hydrocarbon or ring systems Cryptands, Cyclidenes, and Sepulchrates) bound to this macrocyclic ligand, but they do wherein all Binding Sites are composed of not coordinate with the stabilized, high valence Nitrogen (usually amine or imine groups) or metal ion. This ligand and/or attached, Sulfur (usually thiols, mercaptans, or uncoordinating hydrocarbons/rings may or may thiocarbonyls) and are not contained in not have halogen or polarizing or water- Component Heterocyclic Rings (N—S insolubilizing/solubilizing groups attached. Tridentates, N—S Tetradentates, and N—S Hexadentates) N—S Valence Stabilizer #23: Macrocyclic ligands containing a total of five or Five-, or Seven-Membered Macrocyclics, seven heterocyclic rings containing nitrogen or Macrobicyclics, and Macropolycyclics sulfur binding sites. Can include other (including Catapinands, Cryptands, hydrocarbon/ring systems bound to this Cyclidenes, and Sepulchrates) wherein all macrocyclic ligand, but they do not coordinate Binding Sites are composed of Nitrogen or with the stabilized, high valence metal ion. This Sulfur and are contained in Component ligand and/or attached, uncoordinating Heterocyclic Rings (N—S Tridentates, N—S hydrocarbon/rings may or may not have halogen Tetradentates, or N—S Hexadentates) or polarizing or water-insolubilizing groups attached. N—S Valence Stabilizer #24: Macrocyclic ligands containing at least one Five-, Seven-, or Nine-Membered heterocyclic ring. These heterocyclic rings Macrocyclics, Macrobicyclics, and provide nitrogen or sulfur binding sites to Macropolycyclics (including Catapinands, valence stabilize the central metal ion. Other Cryptands, Cyclidenes, and Sepulchrates) amine, imine, thiol, mercapto, or thiocarbonyl wherein all Binding Sites are composed of binding sites can also be included in the Nitrogen or Sulfur and are contained in a macrocyclic ligand, so long as the total number Combination of Heterocyclic Rings and of binding sites is five, seven, or nine. Can Amine, Imine, Thiol, Mercapto, or include other hydrocarbon/ring systems bound Thiocarbonyl Groups (N—S Tridentates, N—S to this macrocyclic ligand, but they do not Tetradentates, or N—S Hexadentates) coordinate with the stabilized, high valence metal ion. This ligand and/or attached, uncoordinating hydrocarbon/rings may or may not have halogen or polarizing or water- insolubilizing groups attached. N—O Valence Stabilizer #1: RC(═NH)OR′, where R and R′ represent H or Imidates, Diimidates, Polyimidates, and any organic functional group wherein the Derivatives of Imidic Acid (N—O Bidentates number of carbon atoms ranges from 0 to 40, and N—O Tetradentates) optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—O Valence Stabilizer #2: RR′NC(═NH)OR″, where R, R′, and R″ Pseudoureas, bis(pseudoureas), and represent H, NH2, or any organic functional poly(pseudoureas) (N—O Bidentates and N— group wherein the number of carbon atoms O Tetradentates) ranges from 0 to 40, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—O Valence Stabilizer #3: RR′NC(═NH)CR″R″′(CO)OR″″, where R, R′, 2-Amidinoacetates, Bis(2-amidinoacetates), R″, R″′, and R″″ represent H, NH2, or any and Poly(2-amidinoacetates) (N—O organic functional group wherein the number of Bidentates and N—O Tetradentates) carbon atoms ranges from 0 to 40, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—O Valence Stabilizer #4: RR′NCONR″R″′, where R, R′, R″, and R″′ Ureas, Bis(ureas), and Poly(ureas), represent H, NH2, or any organic functional including Urylene Complexes (N—O group wherein the number of carbon atoms Bidentates, N—O Tridentates, and N—O ranges from 0 to 40, optionally having halogen Tetradentates) or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—O Valence Stabilizer #5: (NH═)PR(OR′)(OR″), where R, R′, and R″ Phosphonimidic Acid, Bis(phosphonimidic represent H, NH2, or any organic functional acid), Poly(phosphonimidic acid), and group wherein the number of carbon atoms derivatives thereof (N—O Bidentates and N— ranges from 0 to 40, optionally having halogen O Tetradentates) or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms N—O Valence Stabilizer #6: (O═)PR(—NR′R″)(—OR″′) for phosphonamidic Phosphonamidic Acid, Phosphonic acid and (O═)PR(—NR′R″)(—NR″′R″″) for Diamide, Bis(Phosphonamidic Acid), phosphonic diamide, where R, R′, R″, R″′, and Bis(Phosphonic Diamide), R″″ represent H, NH2, or any organic functional Poly(phosphonamidic acid), group wherein the number of carbon atoms poly(phosphonic diamide), and derivatives ranges from 0 to 40, optionally having halogen thereof (N—O Bidentates and N—O or polarizing or water- Tetradentates) insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—O Valence Stabilizer #7: R—C(═O)—CR′═C(—NHR″)R″′, where R, R′, R″, Beta-Ketoamines (N-Substituted 3-amino- and R″′ represent H, or any organic functional 2-propenals), Bis(beta-ketoamines), and group wherein the number of carbon atoms Poly(beta-ketoamines) (N—O Bidentates and ranges from 0 to 40, optionally having halogen N—O Tetradentates) or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—O Valence Stabilizer #8: RR′ —N—C(═O)—CR″═C(—NHR″′)R″″ for 3- 3-Aminoacrylamides (3-Amino-2- aminoacrylamides, and RR′—N—C(═O)—CR″═C(— propenamides), 3,3-Diaminoacrylamides, NHR″′)(—NR″″R″″′) for 3,3- Bis(3-aminoacrylamides), Bis(3,3- diaminoacrylamides, where R, R′, R″, R″′, R″″, diaminoacrylamides), Poly(3- and R″″′ represent H, NH2, or any organic aminoacrylamides), and Poly(3,3- functional group wherein the number of carbon diaminoacrylamides) (N—O Bidentates and atoms ranges from 0 to 40, optionally having N—O Tetradentates) halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—O Valence Stabilizer #9: R—O—C(═O)—CR′═C(—NHR″)R″′ for 3- 3-Aminoacrylic Acids (3-Amino-2- aminoacrylic acids, and R—O—C(═O)—CR′═C(— propenoic acids), 3-Hydroxy-3- NHR″)(—O—R″′) for 3-hydroxy-3-aminoacrylic aminoacrylic acids, Bis(3-aminoacrylic acids, where R, R′, R″, and R″′ represent H, acids), Bis(3-Hydroxy-3-aminoacrylic NH2, or any organic functional group wherein acids), Poly(3-aminoacrylic acids), and the number of carbon atoms ranges from 0 to Poly(3-Hydroxy-3-aminoacrylic acids), and 40, optionally having halogen or polarizing or derivatives thereof (N—O Bidentates and N— water-insolubilizing/solubilizing groups O Tetradentates) attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—O Valence Stabilizer #10: R—C(═O)—N═CHR′, where R′ represents an N-Acyl Benzylidenimines, Bis(N-acyl aromatic derivative (i.e. —C6H5), and R represent benzylidenimines), and Poly(N-acyl H, NH2, or any organic functional group benzylidenimines) (N—O Bidentates and N— wherein the number of carbon atoms ranges O Tetradentates) from 0 to 40, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—O Valence Stabilizer #11: o—(O2N—)(RR′N—)Ar, where Ar represents an 2-Nitroanilines (N—O Bidentates) aromatic group or heterocyclic wherein the number of carbon atoms ranges from 6 to 40, and R and R′ represent H, NH2, or alkyl or aryl hydrocarbon groups wherein the number of carbon atoms range from 0 to 25, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—O Valence Stabilizer #12: o—(NC—(CH2)0-1)(HO—)Ar, where Ar represents 2-Nitrilophenols (N—O Bidentates). Also an aromatic group or heterocyclic wherein the includes acylcyanamides. number of carbon atoms ranges from 6 to 40, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—O Valence Stabilizer #13: Het N+—O−for amine N—oxides, and R—N═N+(—O−)— Amine N—Oxides and Diazine N—Oxides R′ for diazine N—oxides (azoxy compounds), (Azoxy componds) (N—O Bidentates, N—O where Het represents a nitrogen-containing Tridentates, and N—O Tetradentates) heterocyclic derivative wherein the number of carbon atoms ranges from 4 to 40, and R and R′ represent separate or the same aromatic functionalities, both Het and R,R′ optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—O Valence Stabilizer #14: R—C(═O)—NHNR′R″, where R, R′, and R″ Hydrazides, Bis(hydrazides), and represent H or any organic functional group Poly(hydrazides) (N—O Bidentates and N—O wherein the number of carbon atoms ranges Tetradentates) from 0 to 40, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—O Valence Stabilizer #15: RR′—N—C(═O)—NHNR″R″′, where R, R′, and R″ Semicarbazides, Bis(semicarbazides), and represent H or any organic functional group Poly(semicarbazides) (N—O Bidentates, N—O wherein the number of carbon atoms ranges Tetradentates, and N—O Hexadentates) from 0 to 40, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. N—O Valence Stabilizer #16: Macrocyclic ligands containing five, seven, or Five-, Seven-, or Nine-Membered nine binding sites composed of nitrogen and Macrocyclics, Macrobicyclics, and oxygen to valence stabilize the central metal Macropolycyclics (including Catapinands, ion. Can include other hydrocarbon or ring Cryptands, Cyclidenes, and Sepulchrates) systems bound to this macrocyclic ligand, but wherein all Binding Sites are composed of they do not coordinate with the stabilized, high Nitrogen (usually amine or imine groups) or valence metal ion. This ligand and/or attached, Oxygen (usually hydroxy, carboxy, or uncoordinating hydrocarbons/rings may or may carbonyl groups) and are not contained in not have halogen or polarizing or water- Component Heterocyclic Rings (N—O insolubilizing/solubilizing groups attached. Tridentates, N—O Tetradentates, and N—O Hexadentates) N—O Valence Stabilizer #17: Macrocyclic ligands containing a total of five or Five-, or Seven-Membered Macrocyclics, seven heterocyclic rings containing nitrogen or Macrobicyclics, and Macropolycyclics oxygen binding sites. Can include other (including Catapinands, Cryptands, hydrocarbon/ring systems bound to this Cyclidenes, and Sepulchrates) wherein all macrocyclic ligand, but they do not coordinate Binding Sites are composed of Nitrogen or with the stabilized, high valence metal ion. This Oxygen and are contained in Component ligand and/or attached, uncoordinating Heterocyclic Rings (N—O Tridentates, N—O hydrocarbon/rings may or may not have halogen Tetradentates, or N—O Hexadentates) or polarizing or water-insolubilizing groups attached. N—O Valence Stabilizer #18: Macrocyclic ligands containing at least one Five-, Seven-, or Nine-Membered heterocyclic ring. These heterocyclic rings Macrocyclics, Macrobicyclics, and provide nitrogen or oxygen binding sites to Macropolycyclics (including Catapinands, valence stabilize the central metal ion. Other Cryptands, Cyclidenes, and Sepulchrates) amine, imine, hydroxy, carboxy, or carbonyl wherein all Binding Sites are composed of binding sites can also be included in the Nitrogen or Oxygen and are contained in a macrocyclic ligand, so long as the total number Combination of Heterocyclic Rings and of binding sites is five, seven, or nine. Can Amine, Imine, Hydroxy, Carboxy, or include other hydrocarbon/ring systems bound Carbonyl Groups (N—O Tridentates, N—O to this macrocyclic ligand, but they do not Tetradentates, or N—O Hexadentates) coordinate with the stabilized, high valence metal ion. This ligand and/or attached, uncoordinating hydrocarbon/rings may or may not have halogen or polarizing or water- insolubilizing groups attached. S—O Valence Stabilizer #1: RR′—N—C(═S)—NR″—C(═O)—NR″′R″″ for Thiobiurets (Thioimidodicarbonic thiobiurets, and RR′—N—C(═S)—NR″—NH—C(═O)— Diamides), Thioisobiurets, Thiobiureas, NR″′R″″ for thiobiureas, where R, R′, R″, R″′, Thiotriurets, Thiotriureas, Bis(thiobiurets), and R″″ represent H, NH2, or any organic Bis(thioisobiurets), Bis(thiobiureas), functional group wherein the number of carbon Poly(thiobiurets), Poly(thioisobiurets), atoms ranges from 0 to 40, optionally having Poly(thiobiureas) (S—O Bidentates, S—O halogen or polarizing or water- Tridentates, S—O Tetradentates), and (3- insolubilizing/solubilizing groups attached. formamidino thiocarbamides) Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #2: RR′—N—C(═S)—NR″—C(═O)—R″′ for acyl—and Acylthioureas, Aroylthioureas, aroylthioureas, and RR′—N—C(═O)—NR″—C(═S)— Thioacylureas, Thioaroylureas, R″′for thioacyl—and thioaroylureas, where R, Bis(acylthioureas), Bis(aroylthioureas), R′, R″, and R″′ represent H, NH2, or any Bis(thioacylureas), Bis(thioaroylureas), organic functional group wherein the number of Poly(thioacylthioureas), carbon atoms ranges from 0 to 40, optionally Poly(thioaroylthioureas), having halogen or polarizing or water- Poly(thioacylureas), and insolubilizing/solubilizing groups attached. Poly(thioaroylureas) (S—O Bidentates, S—O Ligand can also contain nonbinding N, O, S, or Tridentates, S—O Tetradentates) P atoms. S—O Valence Stabilizer #3: RC(═S)—NR′—C(═O)—R″ for Thioimidodialdehydes, thioimidodialdehydes, and RC(═S)—NR′—NH— Thiohydrazidodialdehydes (thioacyl C(═O)—R″ for thiohydrazidodialdehydes hydrazides), Bis(thioimidodialdehydes), (thioacyl hydrazides), where R, R′, and R″ Bis(thiohydrazidodialdehydes), represent H, NH2, or any organic functional Poly(thioimidodialdehydes), and group wherein the number of carbon atoms Poly(thiohydrazidodialdehydes) (S—O ranges from 0 to 40, optionally having halogen Bidentates, S—O Tridentates, S—O or polarizing or water- Tetradentates) insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #4: R—O—C(═S)—NR′—C(═O)—O—R″or R—S—C(═S)— Thioimidodicarbonic acids, NR′—C(═O)—S—R″ for thioimidodicarbonic acids, Thiohydrazidodicarbonic acids, and R—O—C(═S)—NR′—NH—C(═O)—O—R″ or R—S— Bis(thioimidodicarbonic acids), C(═S)—NR′—NH—C(═O)—S—R″ for Bis(thiohydrazidodicarbonic acids), thiohydrazidodicarbonic acids, where R, R′, and Poly(thioimidodicarbonic acids), R″ represent H, NH2, or any organic functional Poly(thiohydrazidodicarbonic acids) and group wherein the number of carbon atoms derivatives thereof (S—O Bidentates, S—O ranges from 0 to 40, optionally having halogen Tridentates, S—O Tetradentates) or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #5: R—C(═S)—C(═O)—R′ where R and R′ represent H, 1,2-Monothioketones (Monothiolenes, NH2, or any organic functional group wherein Monothio—alpha—ketonates), 1,2,3- the number of carbon atoms ranges from 0 to Monothioketones, 1,2,3-Dithioketones, 40, optionally having halogen or polarizing or Monothiotropolonates, ortho- water-insolubilizing/solubilizing groups Monothioquinones, Bis(1,2- attached. Ligand can also contain nonbinding N, Monothioketones), and Poly(1,2- O, S, or P atoms. Monothioketones) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) S—O Valence Stabilizer #6: RR′—N—C(═S)—S—S—C(═O)—N—R″R″′ for Trithioperoxydicarbonic Diamides, trithioperoxydicarbonic diamides, and RR′—N— Dithioperoxydicarbonic Diamides, C(═O)—S—S—C(═O)—N—R″R″′ for Bis(trithioperoxydicarbonic diamides), dithioperoxydicarbonic diamides, where R, R′, Bis(dithioperoxydicarbonic diamides), R″, R″′ represent H or any organic functional poly(trithioperoxydicarbonic diamides) and group wherein the number of carbon atoms poly(dithioperoxydicarbonic diamides) (S—O ranges from 0 to 40, optionally having halogen Bidentates, S—O Tridentates, S—O or polarizing or water- Tetradentates) insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #7: R—O—C(═S)—S—C(═O)—O—R′, where R and R′ Diithiodicarbonic Acids, represent H, NH2 or any organic functional Bis(dithiodicarbonic acids), group wherein the number of carbon atoms Poly(dithiodicarbonic acids), and ranges from 0 to 40, optionally having halogen derivatives thereof (S—O Bidentates, S—O or polarizing or water- Tridentates, S—O Tetradentates) insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #8: R—O—C(═S)—S—S—C(═O)—O—R′, where R and R′ Trithioperoxydicarbonic Acids, represent H, NH2 or any organic functional Bis(trithioperoxydicarbonic acids), group wherein the number of carbon atoms poly(trithioperoxydicarbonic acids), and ranges from 0 to 40, optionally having halogen derivatives thereof (S—O Bidentates, S—O or polarizing or water- Tridentates, S—O Tetradentates) insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #9: (RR′—N—)(R″R″′—N—)P(═S)—S—S—P(═O)(—N— Monothioperoxydiphosphoramide, R″″R″″′)(—N—R″″″R″″″′), where R, R′, R″, R″′, Bis(monothioperoxyphosphoramide), and R″″, R″″′, R″″″, and R″″″′ represent H, NH2 or Poly(monothioperoxydiphosphoramide) (S—O any organic functional group wherein the Bidentates, S—O Tridentates, S—O number of carbon atoms ranges from 0 to 40, Tetradentates) optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #10: (R—O—)(R′—O—)P(═S)—S—S—P(═O)(—O—R″)(—O— Monothioperoxydiphosphoric Acids, R″′); (R—O—)(R′—S—)P(═S)—S—S—P(═O)(—S—R″)(— Bis(monothioperoxyphosphoric Acids), O—R″′); or (R—S—)(R′—S—)P(═S)—S—S—P(═O)(—S— Poly(monothioperoxydiphosphoric Acids), R″)(—S—R″′), where R, R′, R″, R″′, R″″, R″″′, and derivatives thereof (S—O Bidentates, S—O R″″″, and R″″″′ represent H, NH2or any Tridentates, S—O Tetradentates) organic functional group wherein the number of carbon atoms ranges from 0 to 40, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #11: (R—O—)(R′—)P(═S)—NH—P(═O)(—R″)(—O—R″′); (R— Monothioimidodiphosphonic Acids, S—)(R′—)P(═S)—NH—P(═O)(—R″)(—O—R″′); or (R— Monothiohydrazidodiphosphonic Acids, S—)(R′—)P(═S)—NH—P(═O)(—R″)(—S—R″′) for Bis(monothioimidodiphosphonic Acids), monothioimidodiphosphonic acids, and —NH— Bis(monothiohydrazidodiphosphonic NH—derivatives for Acids), Poly(monothioimidodiphosphonic monothiohydrazidodiphosphonic acids, where Acid), R, R′, R″, and R″′ represent H, NH2or any Poly(monothiohydrazidodiphosphonic organic functional group wherein the number of Acids), and derivatives thereof (S—O carbon atoms ranges from 0 to 40, optionally Bidentates, S—O Tridentates, S—O having halogen or polarizing or water- Tetradentates) insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #12: (RR′—N—)(R″—)P(═S)—NH—P(═O)(—R″′)(—N— Monothioimidodiphosphonamides, R″″R″″′) for monothioimidodiphosphonamides, Monothiohydrazidodiphosphonamides, and —NH—NH—derivatives for Bis(monothioimidodiphosphonamides), monothiohydrazidodiphosphonamides, where R, Bis(monothiohydrazidodiphosphonamidcs) R′, R″, R″′, R″″, and R″″′, represent H, NH2or Poly(monothioimidodiphosphonamides), any organic functional group wherein the and number of carbon atoms ranges from 0 to 40, Poly(monothiohydrazidodiphosphonamides) optionally having halogen or polarizing or (S—O Bidentates, S—O Tridentates, S—O water-insolubilizing/solubilizing groups Tetradentates) attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #13: (RR′—N—)(R″—)P(═S)—S—P(═O)(—R″′)(—N— Monothiodiphosphonamides, R″″R″″′), or (RR′—N—)(R″—)P(═S)—O—P(═O)(— Bis(monothioiphosphonarnides), and R″′)(—N—R″″R″″′), where R, R′, R″, R″′, R″″, Poly(monothiodiphosphonamides) (S—O and R″″′ represent H, NH2or any organic Bidentates, S—O Tridentates, S—O functional group wherein the number of carbon Tetradentates) atoms ranges from 0 to 40, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #14: (R—O—)(R′—)P(═S)—O—P(═O)(—R″)(—O—R″′); (R— Monothiodiphosphonic Acids, O—)(R′—)P(═S)—S—P(═O)(—R″)(—O—R″′); (R—S—) Bis(monothioiphosphonic Acids), (R′—)P(═S)—O—P(═O)(—R″)(—S—R″′); or (R—S—) Poly(monothiodiphosphonic Acids), and (R′—)P(═S)—S—P(═O)(—R″)(—S—R″′), where R, derivatives thereof (S—O Bidentates, S—O R′, R″, and R″′ represent H, NH2or any organic Tridentates, S—O Tetradentates) functional group wherein the number of carbon atoms ranges from 0 to 40, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #15: (RR′—N—)(R″—)P(═S)—S—S—P(═O)(—R″′)(—N— Monothioperoxydiphosphonamide, R″″R″″′), where R, R′, R″, R″′, R″″, and R″″′ Bis(monothioperoxyphosphonamide), and represent H, NH2 or any organic functional Poly(monothioperoxydiphosphonamide) (S—O group wherein the number of carbon atoms Bidentates, S—O Tridentates, S—O ranges from 0 to 40, optionally having halogen Tetradentates) or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #16: (R—O—)(R′—)P(═S)—S—S—P(═O)(—R″)(—O—R″′); or Monothioperoxydiphosphonic Acids, (R—S—)(R′—)P(═S)—S—S—P(═O)(—R″)(—S—R″′), Bis(monothioperoxyphosphonic Acids), where R, R′, R″, and R″′ represent H, NH2 or Poly(monothioperoxydiphosphonic Acids), any organic functional group wherein the and derivatives thereof (S—O Bidentates, S—O number of carbon atoms ranges from 0 to 40, Tridentates, S—O Tetradentates) optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #17: (O═)P(—S—R)(—O—R′)(—O—R″) or (S═)P(—O—R)(—O— Monothiophosphoric Acids R′)(—O—R″), where R, R′, and R″ represent H, (Phosphorothioic Acids), NH2or any organic functional group wherein Bis(monothiophosphoric acids), the number of carbon atoms ranges from 0 to Poly(monothiophosphoric acids), and 40, optionally having halogen or polarizing or derivatives thereof (S—O Bidentates, S—O water-insolubilizing/solubilizing groups Tridentates, S—O Tetradentates) attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #18: (O═)P(—S—S—R)(—O—R′)(—O—R″), where R, R′, Phosphoro(dithioperoxoic) Acids, and R″ represent H, NH2 or any organic Bis[phosphoro(dithioperoxoic) acids], functional group wherein the number of carbon Poly[phosphoro(dithioperoxoic) acids], and atoms ranges from 0 to 40, optionally having derivatives thereof (S—O Bidentates, S—O halogen or polarizing or water- Tridentates, S—O Tetradentates) insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #19: (O═)PR(—S—R′)(—O—R″) or (S═)PR(—O—R′)(—O— Monothiophosphonic Acids R″), where R, R′, and R″ represent H, NH2 or (Phosphonothioic Acids), any organic functional group wherein the Bis(monothiophosphonic Acids), number of carbon atoms ranges from 0 to 40, Poly(monothiophosphonic Acids), and optionally having halogen or polarizing or derivatives thereof (S—O Bidentates, S—O water-insolubilizing/solubilizing groups Tridentates, S—O Tetradentates) attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #20: (O═)PR(—S—S—R′)(—O—R″), where R, R′, and R″ Phosphono(dithioperoxoic) Acids, represent H, NH2 or any organic functional Bis[phosphono(dithioperoxoic) Acids], group wherein the number of carbon atoms Poly[phosphono(dithioperoxoic) Acids], ranges from 0 to 40, optionally having halogen and derivatives thereof (S—O Bidentates, S—O or polarizing or water- Tridentates, S—O Tetradentates) insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #21: R—CR′(—OH)—CH2—C(═S)—R″, where R, R′, and Beta-Hydroxythioketones, Beta- R″ represent H, NH2 or any organic functional Hydroxythioaldehydes, Bis(beta- group wherein the number of carbon atoms hydroxythioketones), Bis(beta- ranges from 0 to 40, optionally having halogen hydroxythioaldehydes), Poly(beta- or polarizing or water- hydroxythioketones), and Poly(beta- insolubilizing/solubilizing groups attached. hydroxythioaldehydes) (S—O Bidentates, S—O Ligand can also contain nonbinding N, O, S, or Tridentates, S—O Tetradentates) P atoms. S—O Valence Stabilizer #22: R—CR′(—SH)—CH2—C(═O)—R″, where R, R′, and Beta-Mercaptoketones, Beta- R″ represent H, NH2 or any organic functional Mercaptoaldehydes, Bis(beta- group wherein the number of carbon atoms mercaptoketones), Bis(beta- ranges from 0 to 40, optionally having halogen mercaptoaldehydes), Poly(beta- or polarizing or water- mereaptoketones), and Poly(beta- insolubilizing/solubilizing groups attached. mercaptoaldehydes) (S—O Bidentates, S—O Ligand can also contain nonbinding N, O, S, or Tridentates, S—O Tetradentates) P atoms. S—O Valence Stabilizer #23: RR′—N—CH(—OH)—NR″—C(═S)—NR″′R″″, where N-(Aminomethylol)thioureas [N- R, R′, R″, R″′, and R″″ represent H, NH2 or any (Aminohydroxymethyl)thioureas], Bis[N- organic functional group wherein the number of (aminomethylol)thioureas], and Poly[N- carbon atoms ranges from 0 to 40, optionally (aminomethylol)thioureas](S—O Bidentates, having halogen or polarizing or water- S—O Tridentates, S—O Tetradentates) insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #24: RR′—N—CH(—SH)—NR″—C(═O)—NR″′R″″, where N-(Aminomethylthiol)ureas [N- R, R′, R″, R″′, and R″″ represent H, NH2 or any (Aminomercaptomethyl)ureas], Bis[N- organic functional group wherein the number of (aminomethylthiol)ureas], and Poly[N- carbon atoms ranges from 0 to 40, optionally (aminomethylthiol)ureas](S—O Bidentates, having halogen or polarizing or water- S—O Tridentates, S—O Tetradentates) insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #25: RR′—N—C(═S)—C(═O)—N—R″R″′, where R, R′, Monothiooxamides, R″, and R″′ represent H, NH2 or any organic Bis(monothiooxamides), and functional group wherein the number of carbon Poly(monothiooxamides) (S—O Bidentates, atoms ranges from 0 to 40, optionally having S—O Tridentates, S—O Tetradentates) halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #26: R—CR′(—SH)—CR″R″′—C(═O)(—O—R″″), where R, Beta-Mercapto Carboxylic Acids, Bis(Beta- R′, R″, R″′, and R″″ represent H, NH2 or any Mercapto Carboxylic Acids), Poly(Beta- organic functional group wherein the number of Mercapto Carboxylic Acids), and carbon atoms ranges from 0 to 40, optionally derivatives thereof (S—O Bidentates, S—O having halogen or polarizing or water- Tridentates, S—O Tetradentates) insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #27: R—CR′(—SH)—CR″R″′—C(═O)(—S—R″″), where R, Beta-Mercapto Thiocarboxylic Acids, R′, R″, R″′, and R″″ represent H, NH2 or any Bis(Beta-Mercapto Thiocarboxylic Acids), organic functional group wherein the number of Poly(Beta-Mercapto Thiocarboxylic Acids), carbon atoms ranges from 0 to 40, optionally and derivatives thereof (S—O Bidentates, S—O having halogen or polarizing or water- Tridentates, S—O Tetradentates) insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #28: R—CR′(—OH)—CR″R″′—C(═O)(—S—R″″), where R, Beta-Hydroxy Thiocarboxylic Acids, R′, R″, R″′, and R″″ represent H, NH2 or any Bis(Beta-Hydroxy Thiocarboxylic Acids), organic functional group wherein the number of Poly(Beta-Hydroxy Thiocarboxylic Acids), carbon atoms ranges from 0 to 40, optionally and derivatives thereof (S—O Bidentates, S—O having halogen or polarizing or water- Tridentates, S—O Tetradentates) insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #29: R—CR′(—SH)—CR″R″′—C(═O)(—NH—R″″), where Beta-Mercapto Carboxamides, Bis(Beta- R, R′, R″, R″′, and R″″ represent H, NH2 or any Mercapto Carboxamides), Poly(Beta- organic functional group wherein the number of Mercapto Carboxamides), and derivatives carbon atoms ranges from 0 to 40, optionally thereof (S—O Bidentates, S—O Tridentates, having halogen or polarizing or water- S—O Tetradentates) insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #30: R—S—R′COOH for S-alkylthiocarboxylic and S- S-Alkylthiocarboxylic Acids, S- arylthiocarboxylic acids, and HOOCR—S— Arylthiocarboxylic Acids, and S,S- R′COOH for S,S-thiobiscarboxylic acids, where thiobiscarboxylic Acids (S—O Bidentates R and R′ represent H or any organic functional and S—O Tridentates) group wherein the number of carbon atoms ranges from 0 to 40, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #31: R—S—S—R′COOH for S-alkyldisulfidocarboxylic S-Alkyldisulfidocarboxylic Acids, S- and S-aryldisulfidocarboxylic acids, and Aryldisulfidocarboxylic Acids, and S,S′— HOOCR—S—S—R′COOH for S,S′- Disulfidobiscarboxylic Acids (S—O disulfidobiscarboxylic acids, where R and R′ Bidentates and S—O Tridentates) represent H or any organic functional group wherein the number of carbon atoms ranges from 0 to 40, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #32: R—C(═O)(—S—R′) for monothiomonocarboxylic Monothiomonocarboxylic Acids, acids, and (R—S—)(O═)C—R′—C(═O)(—S—R″) or (R— Dithiodicarboxylic Acids, S—)(O═)C—R′—C(═O)(—O—R″) for Bis(monothiomonocarboxylic Acids), dithiodicarboxylic acids, where R, R′, and R″ Bis(dithiodicarboxylic acids), represent H, NH2 or any organic functional Poly(monothiomonocarboxylic acids), group wherein the number of carbon atoms Poly(dithiodicarboxylic acids), and ranges from 0 to 40, optionally having halogen derivatives thereof (S—O Bidentates and S—O or polarizing or water- Tetradentates) insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #33: R—O—C(═S)—O—R′, where R, and R′ represent H, Monothiocarbonates and NH2 or any organic functional group wherein Bis(monothiocarbonates) (S—O Bidentates the number of carbon atoms ranges from 0 to and S—O Tetradentates) 40, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #34: RR′N—NR″—C(═O)(SH), where R and R′ Monothiocarbazates (Monothiocarbazides), represent H, NH2 or any organic functional Bis(monothiocarbazates), and group wherein the number of carbon atoms Poly(monothiocarbazates) (S—O Bidentates, ranges from 0 to 40, optionally having halogen S—O Tridentates, and S—O Tetradentates; or or polarizing or water- possibly N—S Bidentates, N—S Tridentates, insolubilizing/solubilizing groups attached. and N—S Tetradentates) Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #35: R—CH(—SH)—CH(—OH)—R′ for alpha-mercapto Mercapto Alcohols and alcohols, R—CH(—SH)—Si(—OR′)x—R″3-x for alpha- Silylmercaptoalcohols, Bis(mercapto silylmercaptoalcohols, R—CH(—SH)—R′—CH(— alcohols and silylmercaptoalcohols), and OH)—R″ for beta-mercapto alcohols, and R—CH(— Poly(mercapto alcohols and SH)—R′—Si(—OR″)x—R″′3-x for beta- silylmercaptoalcohols) (S—O Bidentates, S—O silylmercaptoalcohols, etc., where R, R′, R″, Tridentates, S—O Tetradentates) and R″′ represent H, NH2 or any organic functional group wherein the number of carbon atoms ranges from 0 to 40, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. x = 1-3. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #36: RN═C(OH)(SH), where R represents H, NH2 or Monothiocarbimates, any organic functional group wherein the Bis(monothiocarbimates), and number of carbon atoms ranges from 0 to 40, Poly(monothiocarbimates) (S—O Bidentates, optionally having halogen or polarizing or S—O Tridentates, and S—O Tetradentates) water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #37: R—O—C(—S—R″)—O—R′, where R, R′, and R″ Alkyl-and Aryl-Monothioborates and represent H, NH2 or any organic functional Bis(monothioborates) (S—O Bidentates and group wherein the number of carbon atoms S—O Tetradentates) ranges from 0 to 40, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #38: R—C(—S—R″)—O—R′, where R, R′, and R″ Alkyl-and Aryl-Monothioboronates and represent H, NH2 or any organic functional Bis(monothioboronates) (S—O Bidentates group wherein the number of carbon atoms and S—O Tetradentates) ranges from 0 to 40, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #39: (O═)As(—S—R)(—O—R′)(—O—R″) or (S═)As(—O— Monothioarsonic Acids (Arsonothioic R)(—O—R′)(—O—R″), where R, R′, and R″ Acids), Bis(monothioarsonic acids), represent H, NH2 or any organic functional Poly(monothioarsonic acids), and group wherein the number of carbon atoms derivatives thereof (S—O Bidentates, S—O ranges from 0 to 40, optionally having halogen Tridentates, S—O Tetradentates) or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. S—O Valence Stabilizer #40: Heterocyclic ring(s) containing one or two Heterocyclic Rings containing One or Two sulfur atoms. In addition, ligand contains Sulfur Atoms at least one additional additional oxygen-containing substituents Oxygen Atom Binding Site not in a Ring (usually hydroxy, carboxy, or carbonyl groups) (S—O Bidentates, S—O Tridentates, S—O that constitute O binding sites. Can include Tetradentates, or S—O Hexadentates) other ring systems bound to the heterocyclic ring or to the O-containing substituent, but they do not coordinate with the stabilized, high valence metal ion. Ring(s) can also contain O, N, P, As or Se atoms. This 5-membered ring(s) and/or attached, uncoordinating rings and/or O- containing substituent(s) may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. S—O Valence Stabilizer #41: Heterocyclic ring(s) containing one or two Heterocyclic Rings containing One or Two oxygen atoms. In addition, ligand contains Oxygen Atoms at least one additional additional sulfur-containing substituents Sulfur Atom Binding Site not in a Ring (S—O (usually thio, mercapto, or thiocarbonyl groups) Bidentates, S—O Tridentates, S—O that constitute S binding sites. Can include Tetradentates, or S—O Hexadentates) other ring systems bound to the heterocyclic ring or to the S-containing substituent, but they do not coordinate with the stabilized, high valence metal ion. Ring(s) can also contain O, N, P, As or Se atoms. This 5-membered ring(s) and/or attached, uncoordinating rings and/or S- containing substituent(s) may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. S—O Valence Stabilizer #42: Heterocyclic ring(s) containing one or two Heterocyclic Rings containing One or Two sulfur atoms. In addition, ligand contains Sulfur Atoms at least one additional additional oxygen-containing rings that Oxygen Atom Binding Site in a separate constitute O binding sites. Can include other Ring (S—O Bidentates, S—O Tridentates, S—O ring systems bound to the O-containing Tetradentates, or S—O Hexadentates) heterocyclic rings, but they do not coordinate with the stabilized, high valence metal ion. Ring(s) can also contain O, N, P, As, or Se atoms. This 5-membered ring(s) and/or additional O-containing ring(s) and/or attached, uncoordinating rings may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. S—O Valence Stabilizer #43: Macrocyclic ligands containing two to ten sulfur Two-, Three-, Four-, Five-, Six-, Seven-, or oxygen binding sites to valence stabilize the Eight-, Nine-, and Ten-Membered central metal ion. Can include other Macrocyclics, Macrobicyclics, and hydrocarbon or ring systems bound to this Macropolycyclics (including Catapinands, macrocyclic ligand, but they do not coordinate Cryptands, Cyclidenes, and Sepulchrates) with the stabilized, high valence metal ion. This wherein all Binding Sites are composed of ligand and/or attached, uncoordinating Sulfur (usually thiol, mercapto, or hydrocarbons/rings may or may not have thiocarbonyl groups) or Oxygen (hydroxy, halogen or polarizing or water- carboxy, or carbonyl groups) and are not insolubilizing/solubilizing groups attached. contained in Component Heterocyclic Rings (S—O Bidentates, S—O Tridentates, S—O Tetradentates, and S—O Hexadentates) S—O Valence Stabilizer #44: Macrocyclic ligands containing a total of four to Four-, Five-, Six-, Seven-, Eight-, Nine-, or ten five-membered heterocyclic rings containing Ten-Membered Macrocyclics, sulfur or oxygen binding sites. Can include Macrobicyclics, and Macropolycyclics other hydrocarbon/ring systems bound to this (including Catapinands, Cryptands, macrocyclic ligand, but they do not coordinate Cyclidenes, and Sepulchrates) wherein all with the stabilized, high valence metal ion. This Binding Sites are composed of Sulfur or ligand and/or attached, uncoordinating Oxygen and are contained in Component 5- hydrocarbon/rings may or may not have halogen Membered Heterocyclic Rings (S—O or polarizing or water-insolubilizing groups Tridentates, S—O Tetradentates or S—O attached. Hexadentates) S—O Valence Stabilizer #45: Macrocyclic ligands containing at least one Four-, Five-, Six-, Seven-, Eight-, Nine-, or heterocyclic ring. These heterocyclic rings Ten-Membered Macrocyclics, provide sulfur or oxygen binding sites to Macrobicyclics, and Macropolycyclics valence stabilize the central metal ion. Other (including Catapinands, Cryptands, thiol, mercapto, thiocarbonyl, hydroxy, carboxy, Cyclidenes, and Sepulchrates) wherein all or carbonyl binding sites can also be included in Binding Sites are composed of Sulfur or the macrocyclic ligand, so long as the total Oxygen and are contained in a Combination number of binding sites is four to ten. Can of Heterocyclic Rings and Thiol, Mercapto, include other hydrocarbon/ring systems bound Thiocarbonyl, Hydroxy, Carboxy, and to this macrocyclic ligand, but they do not Carbonyl Groups (S—O Tridentates, S—O coordinate with the stabilized, high valence Tetradentates, or S—O Hexadentates) metal ion. This ligand and/or attached, uncoordinating hydrocarbon/rings may or may not have halogen or polarizing or water- insolubilizing groups attached. S—O Valence Stabilizer #46: Sulfoxides (R—SO—R′), where R and R′ Sulfoxides (S—O Bidentates) represent H or any organic functional group wherein the number of carbon atoms ranges from 0 to 35, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. S—O Valence Stabilizer #47: Sulfones (R—SO2—R′), where R and R′ represent Sulfones (S—O Bidentates) H or any organic functional group wherein the number of carbon atoms ranges from 0 to 35, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. S—O Valence Stabilizer #48: Sulfur dioxide ligands (—SO2) bound directly to Sulfur dioxide (SO2) ligands (S—O the high valence metal ion. Bidentates) N—P Valence Stabilizer #1: [R(—NR′R″)(—PR″′R″″)], [R(—NR′R″)x]1-3P, [R Aminoaryl Phosphines and Iminoaryl (—NR′R″)x]1-3PX, or [R(—PR′R″)x]1-3N, where X = O Phosphines (N—P Bidentates, N—P or S and R, R′, R″, R″′, and R″″ represents Tridentates, and N—P Tetradentates) H, NH2 or any organic functional group wherein the number of carbon atoms ranges from 0 to 35, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, P, O, S, or Se atoms. N—P Valence Stabilizer #2: Five membered heterocyclic ring(s) containing Heterocyclic Rings containing One, Two, one, two, three, or four nitrogen atoms. In Three, or Four Nitrogen Atoms at least one addition, ligand contains additional phosphorus- additional Phosphorus Atom Binding Site containing substituents that constitute P binding not in a Ring (N—P Bidentates, N—P sites. Can include other ring systems bound to Tridentates, N—P Tetradentates, or N—P the heterocyclic ring or to the P-containing Hexadentates) substituent, but they do not coordinate with the stabilized, high valence metal ion. Ring(s) can also contain O, S, or P atoms. This ring(s) and/or attached, uncoordinating rings and/or P- containing substituent(s) may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. N—P Valence Stabilizer #3: Five membered heterocyclic ring(s) containing Heterocyclic Rings containing One, Two, one, two, or three phosphorus atoms. In or Three Phosphorus Atoms at least one addition, ligand contains additional nitrogen- additional Nitrogen Atom Binding Site not containing substituents (usually amines, imines, in a Ring (N—P Bidentates, N—P Tridentates, or hydrazides) that constitute N binding sites. N—P Tetradentates, or N—P Hexadentates) Can include other ring systems bound to the heterocyclic ring or to the N-containing substituent, but they do not coordinate with the stabilized, high valence metal ion. Ring(s) can also contain O, S, or P atoms. This ring(s) and/or attached, uncoordinating rings and/or N- containing substituent(s) may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. N—P Valence Stabilizer #4: Heterocyclic ring(s) containing one, two, three, Heterocyclic Rings containing One, Two, or four nitrogen atoms. In addition, ligand Three, or Four Nitrogen Atoms at least one contains additional phosphorus-containing rings additional Phosphorus Atom Binding Site that constitute P binding sites. Can include in a Separate Ring (N—P Bidentates, N—P other ring systems bound to the N- or P- Tridentates, N—P Tetradentates) containing heterocyclic rings, but they do not coordinate with the stabilized, high valence metal ion. Ring(s) can also contain O, S, or P atoms. This ring(s) and/or additional P- containing ring(s) and/or attached, uncoordinating rings may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. N—P Valence Stabilizer #5: Macrocyclic ligands containing two, three, four, Two-, Three-, Four-, Five-, Six-, Seven-, five, six, seven, eight, nine, or ten binding sites Eight-, Nine-, and Ten-Membered composed of nitrogen and phosphorus to Macrocyclics, Macrobicyclics, and valence stabilize the central metal ion. Can Macropolycyclics (including Catapinands, include other hydrocarbon or ring systems Cryptands, Cyclidenes, and Sepulchrates) bound to this macrocyclic ligand, but they do wherein all Binding Sites are composed of not coordinate with the stabilized, high valence Nitrogen (usually amine or imine groups) or metal ion. This ligand and/or attached, Phosphorus and are not contained in uncoordinating hydrocarbons/rings may or may Component Heterocyclic Rings (N—P not have halogen or polarizing or water- Bidentates, N—P Tridentates, N—P insolubilizing/solubilizing groups attached. Tetradentates, and N—P Hexadentates) N—P Valence Stabilizer #6: Macrocyclic ligands containing a total of four, Four-, Five-, Six-, Seven-, Eight-, Nine-, or five, six, seven, eight, nine, or ten heterocyclic Ten-Membered Macrocyclics, rings containing nitrogen or phosphorus binding Macrobicyclics, and Macropolycyclics sites. Can include other hydrocarbon/ring (including Catapinands, Cryptands, systems bound to this macrocyclic ligand, but Cyclidenes, and Sepulchrates) wherein all they do not coordinate with the stabilized, high Binding Sites are composed of Nitrogen or valence metal ion. This ligand and/or attached, Phosphorus and are contained in uncoordinating hydrocarbon/rings may or may Component Heterocyclic Rings (N—P not have halogen or polarizing or water- Bidentates, N—P Tridentates, N—P insolubilizing groups attached. Tetradentates, or N—P Hexadentates) N—P Valence Stabilizer #7: Macrocyclic ligands containing at least one Four-, Five-, Six-, Seven-, Eight-, Nine-, or heterocyclic ring. These heterocyclic rings Ten-Membered Macrocyclics, provide nitrogen or phosphorus binding sites to Macrobicyclics, and Macropolycyclics valence stabilize the central metal ion. Other (including Catapinands, Cryptands, amine, imine, or phosphine binding sites can Cyclidenes, and Sepulchrates) wherein all also be included in the macrocyclic ligand, so Binding Sites are composed of Nitrogen or long as the total number of binding sites is four, Phosphorus and are contained in a five, six, seven, eight, nine, or ten. Can include Combination of Heterocyclic Rings and other hydrocarbon/ring systems bound to this Amine, Imine, and Phosphine Groups (N—P macrocyclic ligand, but they do not coordinate Bidentates, N—P Tridentates, N—P with the stabilized, high valence metal ion. This Tetradentates, or N—P Hexadentates) ligand and/or attached, uncoordinating hydrocarbon/rings may or may not have halogen or polarizing or water-insolubilizing groups attached. S—P Valence Stabilizer #1: [R(—SR′)x]1-3P, [R(—SR′)x]1-3PX, [R(—PR′R″) Thioaryl Phosphines (S—P Bidentates, S—P (—SR″′)], [R(—PR′R″)(—S—S—R″′)], [R(—PR′R″) Tridentates, and S—P Tetradentates) (—C(═S)R″′], [R(—PR′R″)x]2S, [R(—PR′R″)x]2-3 R″′(—SR″′)y, [R(—SR′)x]2-3R″(—PR″′R″″)y, [R(— PR′R″)x]2S2, and [R(—PR′R″)x]2R″′(C(═S))yR″″, where X = O or S, and R, R′, R″, R″′, and R″″ represent H, NH2, or any organic functional group wherein the number of carbon atoms ranges from 0 to 40, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached, and x = 1-2 and y = 1-4. Ligand can also contain nonbinding N, O, S, or P atoms. S—P Valence Stabilizer #2: Heterocyclic ring(s) containing one or two Heterocyclic Rings containing One or Two sulfur atoms. In addition, ligand contains Sulfur Atoms at least one additional additional phosphorus-containing substituents Phosphorus Atom Binding Site not in a that constitute P binding sites. Can include Ring (P—S Bidentates, P—S Tridentates, P—S other ring systems bound to the heterocyclic Tetradentates, or P—S Hexadentates) ring or to the P-containing substituent, but they do not coordinate with the stabilized, high valence metal ion. Ring(s) can also contain O, S, or P atoms. This ring(s) and/or attached, uncoordinating rings and/or P-containing substituent(s) may or may not have halogen or polarizing or water-insolubilizing/solubilizing groups attached. S—P Valence Stabilizer #3: Heterocyclic ring(s) containing one, two, or Heterocyclic Rings containing One, Two, three phosphorus atoms. In addition, ligand or Three Phosphorus Atoms at least one contains additional sulfur-containing additional Sulfur Atom Binding Site not in substituents (usually thiol, mercapto, or a Ring (S—P Bidentates, S—P Tridentates, S—P thiocarbonyl groups) that constitute S binding P Tetradentates, or S—P Hexadentates) sites. Can include other ring systems bound to the heterocyclic ring or to the S-containing substituent, but they do not coordinate with the stabilized, high valence metal ion. Ring(s) can also contain O, S, or P atoms. This ring(s) and/or attached, uncoordinating rings and/or S- containing substituent(s) may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. S—P Valence Stabilizer #4: Heterocyclic ring(s) containing one or two Heterocyclic Rings containing One or Two sulfur atoms. In addition, ligand contains Sulfur Atoms at least one additional additional phosphorus-containing rings that Phosphorus Atom Binding Site in a constitute P binding sites. Can include other Separate Ring (S—P Bidentates, S—P ring systems bound to the S- or P-containing Tridentates, S—P Tetradentates) heterocyclic rings, but they do not coordinate with the stabilized, high valence metal ion. Ring(s) can also contain O, S, or P atoms. This ring(s) and/or additional P-containing ring(s) and/or attached, uncoordinating rings may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. S—P Valence Stabilizer #5: Macrocyclic ligands containing two, three, four, Two-, Three-, Four-, Five-, Six-, Seven-, five, six, seven, eight, nine, or ten binding sites Eight-, Nine-, and Ten-Membered composed of sulfur and phosphorus to valence Macrocyclics, Macrobicyclics, and stabilize the central metal ion. Can include other Macropolycyclics (including Catapinands, hydrocarbon or ring systems bound to this Cryptands, Cyclidenes, and Sepulchrates) macrocyclic ligand, but they do not coordinate wherein all Binding Sites are composed of with the stabilized, high valence metal ion. This Sulfur (usually thiol, mercapto, or ligand and/or attached, uncoordinating thiocarbonyl groups) or Phosphorus and are hydrocarbons/rings may or may not have not contained in Component Heterocyclic halogen or polarizing or water- Rings (S—P Bidentates, S—P Tridentates, S—P insolubilizing/solubilizing groups attached. Tetradentates, and S—P Hexadentates) S—P Valence Stabilizer #6: Macrocyclic ligands containing a total of four, Four-, Five-, Six-, Seven-, Eight-, Nine-, or five, six, seven, eight, nine, or ten heterocyclic Ten-Membered Macrocyclics, rings containing sulfur or phosphorus binding Macrobicyclics, and Macropolycyclics sites. Can include other hydrocarbon/ring (including Catapinands, Cryptands, systems bound to this macrocyclic ligand, but Cyclidenes, and Sepulchrates) wherein all they do not coordinate with the stabilized, high Binding Sites are composed of Sulfur or valence metal ion. This ligand and/or attached, Phosphorus and are contained in uncoordinating hydrocarbon/rings may or may Component Heterocyclic Rings (S—P not have halogen or polarizing or water- Bidentates, S—P Tridentates, S—P insolubilizing groups attached. Tetradentates, or S—P Hexadentates) S—P Valence Stabilizer #7: Macrocyclic ligands containing at least one Four-, Five-, Six-, Seven-, Eight-, Nine-, or heterocyclic ring. These heterocyclic rings Ten-Membered Macrocyclics, provide sulfur or phosphorus binding sites to Macrobicyclics, and Macropolycyclics valence stabilize the central metal ion. Other (including Catapinands, Cryptands, thiol, mercapto, or thiocarbonyl, or phosphine Cyclidenes, and Sepulchrates) wherein all binding sites can also be included in the Binding Sites are composed of Sulfur or macrocyclic ligand, so long as the total number Phosphorus and are contained in a of binding sites is four, five, six, seven, eight, Combination of Heterocyclic Rings and nine, or ten. Can include other Thiol, Mercapto, Thiocarbonyl or hydrocarbon/ring systems bound to this Phosphine Groups (S—P Bidentates, S—P macrocyclic ligand, but they do not coordinate Tridentates, S—P Tetradentates, or S—P with the stabilized, high valence metal ion. This Hexadentates) ligand and/or attached, uncoordinating hydrocarbon/rings may or may not have halogen or polarizing or water-insolubilizing groups attached. P—O Valence Stabilizer #1: [R(—OR′)x]1-3P, [R(—OR′)x]1-3PX, [R(—PR′R″(— Hydroxyaryl Phosphines (P—O Bidentates, OR″′)], [R(—PR′R″)(—C(═O)R″′], [R(— P—O Tridentates, and P—O Tetradentates) PR′R″)x]2O, [R(—PR′R″)x]2-3R″′(—OR″″)y, [R(— OR′)x]2-3R″(—PR″′R″″)y, and [R(— PR′R″)x]2R″′(C(═O))yR″″, where X = O or S, and R, R′, R″,and R″′, and R″″ represent H, NH2, or any organic functional group wherein the number of carbon atoms ranges from 0 to 40, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached, and x = 1-2 and y = 1-4. Ligand can also contain nonbinding N, O, S, or P atoms. P—O Valence Stabilizer #2: Heterocyclic ring(s) containing one or two Heterocyclic Rings containing One or Two oxygen atoms. In addition, ligand contains Oxygen Atoms at least one additional additional phosphorus-containing substituents Phosphorus Atom Binding Site not in a that constitute P binding sites. Can include Ring (P—O Bidentates, P—O Tridentates, P—O other ring systems bound to the heterocyclic Tetradentates, or P—O Hexadentates) ring or to the P-containing substituent, but they do not coordinate with the stabilized, high valence metal ion. Ring(s) can also contain O, S, or P atoms. This ring(s) and/or attached, uncoordinating rings and/or P-containing substituent(s) may or may not have halogen or polarizing or water-insolubilizing/solubilizing groups attached. P—O Valence Stabilizer #3: Heterocyclic ring(s) containing one, two, or Heterocyclic Rings containing One, Two, three phosphorus atoms. In addition, ligand or Three Phosphorus Atoms at least one contains additional oxygen-containing additional Oxygen Atom Binding Site not substituents (usually hydroxy, carboxy, or in a Ring (P—O Bidentates, P—O Tridentates, carbonyl groups) that constitute O binding sites. P—O Tetradentates, or P—O Hexadentates) Can include other ring systems bound to the heterocyclic ring or to the O-containing substituent, but they do not coordinate with the stabilized, high valence metal ion. Ring(s) can also contain O, S, or P atoms. This ring(s) and/or attached, uncoordinating rings and/or O- containing substituent(s) may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. P—O Valence Stabilizer #4: Heterocyclic ring(s) containing one or two Heterocyclic Rings containing One or Two oxygen atoms. In addition, ligand contains Oxygen Atoms at least one additional additional phosphorus-containing rings that Phosphorus Atom Binding Site in a constitute P binding sites. Can include other Separate Ring (P—O Bidentates, P—O ring systems bound to the O- or P-containing Tridentates, P—O Tetradentates) heterocyclic rings, but they do not coordinate with the stabilized, high valence metal ion. Ring(s) can also contain O, S, or P atoms. This ring(s) and/or additional P-containing ring(s) and/or attached, uncoordinating rings may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. P—O Valence Stabilizer #5: Macrocyclic ligands containing two, three, four, Two-, Three-, Four-, Five-, Six-, Seven-, five, six, seven, eight, nine, or ten binding sites Eight-, Nine-, and Ten-Membered composed of oxygen and phosphorus to valence Macrocyclics, Macrobicyclics, and stabilize the central metal ion. Can include other Macropolycyclics (including Catapinands, hydrocarbon or ring systems bound to this Cryptands, Cyclidenes, and Sepulchrates) macrocyclic ligand, but they do not coordinate wherein all Binding Sites are composed of with the stabilized, high valence metal ion. This Oxygen (usually hydroxy, carboxy, or ligand and/or attached, uncoordinating carbonyl groups) or Phosphorus and are not hydrocarbons/rings may or may not have contained in Component Heterocyclic halogen or polarizing or water- Rings (P—O Bidentates, P—O Tridentates, P—O insolubilizing/solubilizing groups attached. Tetradentates, and P—O Hexadentates) P—O Valence Stabilizer #6: Macrocyclic ligands containing a total of four, Four-, Five-, Six-, Seven-, Eight-, Nine-, or five, six, seven, eight, nine, or ten heterocyclic Ten-Membered Macrocyclics, rings containing oxygen or phosphorus binding Macrobicyclics, and Macropolycyclics sites. Can include other hydrocarbon/ring (including Catapinands, Cryptands, systems bound to this macrocyclic ligand, but Cyclidenes, and Sepulchrates) wherein all they do not coordinate with the stabilized, high Binding Sites are composed of Oxygen or valence metal ion. This ligand and/or attached, Phosphorus and are contained in uncoordinating hydrocarbon/rings may or may Component Heterocyclic Rings (P—O not have halogen or polarizing or water- Bidentates, P—O Tridentates, P—O insolubilizing groups attached. Tetradentates, or P—O Hexadentates) P—O Valence Stabilizer #7: Macrocyclic ligands containing at least one Four-, Five-, Six-, Seven-, Eight-, Nine-, or heterocyclic ring. These heterocyclic rings Ten-Membered Macrocyclics, provide oxygen or phosphorus binding sites to Macrobicyclics, and Macropolycyclics valence stabilize the central metal ion. Other (including Catapinands, Cryptands, hydroxy, carboxy, carbonyl, or phosphine Cyclidenes, and Sepulchrates) wherein all binding sites can also be included in the Binding Sites are composed of Oxygen or macrocyclic ligand, so long as the total number Phosphorus and are contained in a of binding sites is four, five, six, seven, eight, Combination of Heterocyclic Rings and nine, or ten. Can include other Hydroxy, Carboxy, Carbonyl or Phosphine hydrocarbon/ring systems bound to this Groups (P—O Bidentates, P—O Tridentates, macrocyclic ligand, but they do not coordinate P—O Tetradentates, or P—O Hexadentates) with the stabilized, high valence metal ion. This ligand and/or attached, uncoordinating hydrocarbon/rings may or may not have halogen or polarizing or water-insolubilizing groups attached. As Valence Stabilizer #1: AsH3, AsH2R, AsHR2, where R represents H or Monoarsines (As Monodentates) wherein at any organic functional group wherein the least one Arsenic Atom is a Binding Site number of carbon atoms ranges from 0 to 25, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, P, As, O, S, or Se atoms. As Valence Stabilizer #2: R′—As—R—As—R″, where R, R′, and R″ represent Diarsines (an As—As Bidentate) wherein at H or any organic functional group wherein the least one Arsenic Atom is a Binding Site number of carbon atoms ranges from 0 to 25, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, P, As, O, S, or Se atoms. As Valence Stabilizer #3: R—As—R′—As—R″—As—R″′, where R, R′, R″, and Triarsines (either As—As Bidentates or As— R″′ represent H or any organic functional group As Tridentates) wherein at least one wherein the number of carbon atoms ranges Arsenic Atom is a Binding Site from 0 to 25, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, P, As, O, S, or Se atoms. As Valence Stabilizer #4: R—As—R′—As—R″—As—R″′—As—R″″, where R, R′, Tetraarsines (As—As Bidentates, As—As R″, R″′, and R″″ represent H or any organic Tridentates, or As—As Tetradentates) functional group wherein the number of carbon wherein at least one Arsenic Atom is a atoms ranges from 0 to 25, optionally having Binding Site halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, P, As, O, S, or Se atoms. As Valence Stabilizer #5: R—As—R′—As—R″—As—R″′—As—R″″—As—R″″′, Pentaarsines (As—As Bidentates, As—As where R, R′, R″, R″′, R″″, and R″″′ represent H Tridentates, or As—As Tetradentates) or any organic functional group wherein the wherein at least one Arsenic Atom is a number of carbon atoms ranges from 0 to 25, Binding Site optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, P, As, O, S, or Se atoms. As Valence Stabilizer #6: R—As—R′—As—R″—As—R″′—As—R″″—As—R″″′—As— Hexaarsines (As—As Bidentates, As—As R″″″, where R, R′, R″, R″′, R″″, R″″′, and Tridentates, As—As Tetradentates, or As—As R″″″ represent H or any organic functional Hexadentates) wherein at least one Arsenic group wherein the number of carbon atoms Atom is a Binding Site ranges from 0 to 25, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, P, As, O, S, or Se atoms. As Valence Stabilizer #7: Five membered heterocyclic ring containing just Five-Membered Heterocyclic Rings one arsenic binding site. Can include other ring containing One Arsenic Atom wherein the systems bound to this heterocyclic ring, but they Arsenic Atom is the Binding Site (As do not coordinate with the stabilized, high Monodentates) valence metal ion. Ring can also contain O, S, N, P, or Se atoms. This 5-membered ring and/or attached, uncoordinating rings may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. As Valence Stabilizer #8: Six membered heterocyclic ring containing just Six-Membered Heterocyclic Rings one arsenic binding site. Can include other ring containing One Arsenic Atom wherein the systems bound to this heterocyclic ring, but they Arsenic Atom is the Binding Site (As do not coordinate with the stabilized, high Monodentates) valence metal ion. Ring can also contain O, S, N, P, or Se atoms. This 6-membered ring and/or attached, uncoordinating rings may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. As Valence Stabilizer #9: Five membered heterocyclic ring(s) containing Five-Membered Heterocyclic Rings one arsenic atom. In addition, ligand contains containing One Arsenic Atom and having at additional arsenic-containing substituents least one additional Arsenic Atom Binding (usually arsines) that constitute As binding sites. Site not in a Ring (As Monodentates, As—As Can include other ring systems bound to the Bidentates, As—As Tridentates, As—As heterocyclic ring or to the As-containing Tetradentates, or As—As Hexadentates) substituent, but they do not coordinate with the stabilized, high valence metal ion. Ring(s) can also contain O, N, S, P or Se atoms. This 5- membered ring(s) and/or attached, uncoordinating rings and/or As-containing substituent(s) may or may not have halogen or polarizing or water-insolubilizing/solubilizing groups attached. As Valence Stabilizer #10: Six membered heterocyclic ring(s) containing Six-Membered Heterocyclic Rings one arsenic atom. In addition, ligand contains containing One Arsenic Atom and having at additional arsenic-containing substituents least one additional Arsenic Atom Binding (usually arsines) that constitute As binding sites. Site not in a Ring (As Monodentates, As—As Can include other ring systems bound to the Bidentates, As—As Tridentates, As—As heterocyclic ring or to the As-containing Tetradentates, or As—As Hexadentates) substituent, but they do not coordinate with the stabilized, high valence metal ion. Ring(s) can also contain O, N, S, P or Se atoms. This 6- membered ring(s) and/or attached, uncoordinating rings and/or As-containing substituent(s) may or may not have halogen or polarizing or water-insolubilizing/solubilizing groups attached. As Valence Stabilizer #11: Five membered heterocyclic ring(s) containing Five-Membered Heterocyclic Rings one arsenic atom. In addition, ligand contains containing One Arsenic Atom and having at additional arsenic-containing rings that least one additional Arsenic Atom Binding constitute As binding sites. Can include other Site in a separate Ring (As Monodentates, ring systems bound to the As-containing As—As Bidentates, As—As Tridentates, As— heterocyclic rings, but they do not coordinate As Tetradentates, or As—As Hexadentates) with the stabilized, high valence metal ion. Ring(s) can also contain O, N, S, P, or Se atoms. This 5-membered ring(s) and/or additional As-containing ring(s) and/or attached, uncoordinating rings may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. As Valence Stabilizer #12: Six membered heterocyclic ring(s) containing Six-Membered Heterocyclic Rings one arsenic atom. In addition, ligand contains containing One Arsenic Atom and having at additional arsenic-containing rings that least one additional Arsenic Atom Binding constitute As binding sites. Can include other Site in a separate Ring (As Monodentates, ring systems bound to the As-containing As—As Bidentates, As—As Tridentates, As— heterocyclic rings, but they do not coordinate As Tetradentates, or As—As Hexadentates) with the stabilized, high valence metal ion. Ring(s) can also contain O, N, S, P, or Se atoms. This 6-membered ring(s) and/or additional As-containing ring(s) and/or attached, uncoordinating rings may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. As Valence Stabilizer #13: Macrocyclic ligands containing two, three, four, Two-, Three-, Four-, and Six-Membered or six arsenic binding sites to valence stabilize Macrocyclics, Macrobicyclics, and the central metal ion. Can include other Macropolycyclics (including Catapinands, hydrocarbon or ring systems bound to this Cryptands, Cyclidenes, and Sepulchrates) macrocyclic ligand, but they do not coordinate wherein all Binding Sites are composed of with the stabilized, high valence metal ion. This Arsenic and are not contained in ligand and/or attached, uncoordinating Component Heterocyclic Rings (As—As hydrocarbons/rings may or may not have Bidentates, As—As Tridentates, As—As halogen or polarizing or water- Tetradentates, and As—As Hexadentates) insolubilizing/solubilizing groups attached. As Valence Stabilizer #14: Macrocyclic ligands containing a total of four or Four-, or Six-Membered Macrocyclics, six five-membered heterocyclic rings containing Macrobicyclics, and Macropolycyclics arsenic binding sites. Can include other (including Catapinands, Cryptands, hydrocarbon/ring systems bound to this Cyclidenes, and Sepulchrates) wherein all macrocyclic ligand, but they do not coordinate Binding Sites are composed of Arsenic and with the stabilized, high valence metal ion. This are contained in Component 5-Membered ligand and/or attached, uncoordinating Heterocyclic Rings (As—As Tridentates, As— hydrocarbon/rings may or may not have halogen As Tetradentates, or As—As Hexadentates) or polarizing or water-insolubilizing groups attached. As Valence Stabilizer #15: Macrocyclic ligands containing at least one 5- Four-, or Six-Membered Macrocyclics, membered heterocyclic ring. These Macrobicyclics, and Macropolycyclics heterocyclic rings provide arsenic binding sites (including Catapinands, Cryptands, to valence stabilize the central metal ion. Other Cyclidenes, and Sepulchrates) wherein all arsine binding sites can also be included in the Binding Sites are composed of Arsenic and macrocyclic ligand, so long as the total number are contained in a Combination of 5- of binding sites is four or eight. Can include Membered Heterocyclic Rings and Arsine other hydrocarbon/ring systems bound to this Groups (As—As Tridentates, As—As macrocyclic ligand, but they do not coordinate Tetradentates, or As—As Hexadentates) with the stabilized, high valence metal ion. This ligand and/or attached, uncoordinating hydrocarbon/rings may or may not have halogen or polarizing or water-insolubilizing groups attached. As Valence Stabilizer #16: Macrocyclic ligands containing a total of four or Four-, or Six-Membered Macrocyclics, six six-membered heterocyclic rings containing Macrobicyclics, and Macropolycyclics arsenic binding sites. Can include other (including Catapinands, Cryptands, hydrocarbon/ring systems bound to this Cyclidenes, and Sepulchrates) wherein all macrocyclic ligand, but they do not coordinate Binding Sites are composed of Arsenic and with the stabilized, high valence metal ion. This are contained in Component 6-Membered ligand and/or attached, uncoordinating Heterocyclic Rings (As—As Tridentates, As— hydrocarbon/rings may or may not have halogen As Tetradentates, or As—As Hexadentates) or polarizing or water-insolubilizing groups attached. As Valence Stabilizer #17: Macrocyclic ligands containing at least one 6- Four-, or Six-Membered Macrocyclics, membered heterocyclic ring. These Macrobicyclics, and Macropolycyclics heterocyclic rings provide arsenic binding sites (including Catapinands, Cryptands, to valence stabilize the central metal ion. Other Cyclidenes, and Sepulchrates) wherein all arsine binding sites can also be included in the Binding Sites are composed of Arsenic and macrocyclic ligand, so long as the total number are contained in a Combination of 6- of binding sites is four or six. Can include other Membered Heterocyclic Rings and Arsine hydrocarbon/ring systems bound to this Groups (As—As Tridentates, As—As macrocyclic ligand, but they do not coordinate Tetradentates, or As—As Hexadentates) with the stabilized, high valence metal ion. This ligand and/or attached, uncoordinating hydrocarbon/rings may or may not have halogen or polarizing or water-insolubilizing groups attached. Se Valence Stabilizer #1: SeH2, SeHR, SeR2, where R represents H or any Monoselenoethers (Se Monodentates) organic functional group wherein the number of wherein at least one Selenium Atom is a carbon atoms ranges from 0 to 25, optionally Binding Site having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, P, O, S, or Se atoms. Se Valence Stabilizer #2: R—Se—R′—Se—R″, where R, R′, and R″ represents Diselenoethers (Se—Se Bidentates) wherein H or any organic functional group wherein the at least one Selenium Atom is a Binding number of carbon atoms ranges from 0 to 25, Site optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, P, O, S, or Se atoms. Se Valence Stabilizer #3: R—Se—R′—Se—R″—Se—R″′, where R, R′, R″, and Triselenoethers (Se—Se Bidentates or Se—Se R″′ represents H or any organic functional Tridentates) wherein at least one Selenium group wherein the number of carbon atoms Atom is a Binding Site ranges from 0 to 25, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, P, O, S, or Se atoms. Se Valence Stabilizer #4: R—Se—R′—Se—R″—Se—R″′—Se—R″″, where R,R′, Tetraselenoethers (Se—Se Bidentates, Se—Se R″, R″′, and R″″ represents H or any organic Tridentates, or Se—Se Tetradentates) functional group wherein the number of carbon wherein at least one Selenium Atom is a atoms ranges from 0 to 25, optionally having Binding Site halogen or polarizing or water- insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, P, O, S, or Se atoms. Se Valence Stabilizer #5: Five membered heterocyclic ring containing one Five-Membered Heterocyclic Rings or two selenium atoms, both of which may containing One or Two Selenium Atoms function as binding sites. Can include other wherein at least one Selenium Atom is a ring systems bound to this heterocyclic ring, but Binding Site (Se Monodentates or Se—Se they do not coordinate with the stabilized, high Bidentates) valence metal ion. Ring can also contain O, N, P, As, or S atoms. This 5-membered ring and/or attached, uncoordinating rings may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. Se Valence Stabilizer #6: Six membered heterocyclic ring containing one Six-Membered Heterocyclic Rings or two selenium atoms, both of which may containing One or Two Selenium Atoms function as binding sites. Can include other wherein at least one Selenium Atom is a ring systems bound to this heterocyclic ring, but Binding Site (Se Monodentates or Se—Se they do not coordinate with the stabilized, high Bidentates) valence metal ion. Ring can also contain O, N, P, As, or S atoms. This 5-membered ring and/or attached, uncoordinating rings may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. Se Valence Stabilizer #7: Five membered heterocyclic ring(s) containing Five-Membered Heterocyclic Rings one selenium atom. In addition, ligand contains containing One Selenium Atom and having additional selenium-containing substituents at least one additional Selenium Atom (usually selenols or selenoethers) that constitute Binding Site not in a Ring (Se Se binding sites. Can include other ring Monodentates, Se—Se Bidentates, Se—Se systems bound to the heterocyclic ring or to the Tridentates, Se—Se Tetradentates, or Se—Se Se-containing substituent, but they do not Hexadentates) coordinate with the stabilized, high valence metal ion. Ring(s) can also contain O, N, P, As or S atoms. This 5-membered ring(s) and/or attached, uncoordinating rings and/or Se- containing substituent(s) may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. Se Valence Stabilizer #8: Six membered heterocyclic ring(s) containing Six-Membered Heterocyclic Rings one selenium atom. In addition, ligand contains containing One Selenium Atom and having additional selenium-containing substituents at least one additional Selenium Atom (usually selenols or selenoethers) that constitute Binding Site not in a Ring (Se Se binding sites. Can include other ring Monodentates, Se—Se Bidentates, Se—Se systems bound to the heterocyclic ring or to the Tridentates, Se—Se Tetradentates, or Se—Se Se-containing substituent, but they do not Hexadentates) coordinate with the stabilized, high valence metal ion. Ring(s) can also contain O, N, P, As or S atoms. This 6-membered ring(s) and/or attached, uncoordinating rings and/or Se- containing substituent(s) may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. Se Valence Stabilizer #9: Five membered heterocyclic ring(s) containing Five-Membered Heterocyclic Rings one selenium atom. In addition, ligand contains containing One Selenium Atom and having additional selenium-containing rings that at least one additional Selenium Atom constitute Se binding sites. Can include other Binding Site in a separate Ring (Se ring systems bound to the Se-containing Monodentates, Se—Se Bidentates, Se—Se heterocyclic rings, but they do not coordinate Tridentates, Se—Se Tetradentates, or Se—Se with the stabilized, high valence metal ion. Hexadentates) Ring(s) can also contain O, N, P, As, or S atoms. This 5-membered ring(s) and/or additional Se-containing ring(s) and/or attached, uncoordinating rings may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. Se Valence Stabilizer #10: Six membered heterocyclic ring(s) containing Six-Membered Heterocyclic Rings one selenium atom. In addition, ligand contains containing One Selenium Atom and having additional selenium-containing rings that at least one additional Selenium Atom constitute Se binding sites. Can include other Binding Site in a separate Ring (Se ring systems bound to the Se-containing Monodentates, Se—Se Bidentates, Se—Se heterocyclic rings, but they do not coordinate Tridentates, Se—Se Tetradentates, or Se—Se with the stabilized, high valence metal ion. Hexadentates) Ring(s) can also contain O, N, P, As, or S atoms. This 6-membered ring(s) and/or additional Se-containing ring(s) and/or attached, uncoordinating rings may or may not have halogen or polarizing or water- insolubilizing/solubilizing groups attached. Se Valence Stabilizer #11: Macrocyclic ligands containing two, three, four, Two-, Three-, Four-, or Six-Membered or six selenium binding sites to valence stabilize Macrocyclics, Macrobicyclics, and the central metal ion. Can include other Macropolycyclics (including Catapinands, hydrocarbon or ring systems bound to this Cryptands, Cyclidenes, and Sepulchrates) macrocyclic ligand, but they do not coordinate wherein all Binding Sites are composed of with the stabilized, high valence metal ion. This Selenium (usually selenol or selenoether ligand and/or attached, uncoordinating groups) and are not contained in hydrocarbons/rings may or may not have Component Heterocyclic Rings (Se—Se halogen or polarizing or water- Bidentates, Se—Se Tridentates, Se—Se insolubilizing/solubilizing groups attached. Tetradentates, or Se—Se Hexadentates) Se Valence Stabilizer #12: Macrocyclic ligands containing a total of four or Four-, or Six-Membered Macrocyclics, six five-membered heterocyclic rings containing Macrobicyclics, and Macropolycyclics selenium binding sites. Can include other (including Catapinands, Cryptands, hydrocarbon/ring systems bound to this Cyclidenes, and Sepulchrates) wherein all macrocyclic ligand, but they do not coordinate Binding Sites are composed of Selenium with the stabilized, high valence metal ion. This and are contained in Component 5- ligand and/or attached, uncoordinating Membered Heterocyclic Rings (Se—Se hydrocarbon/rings may or may not have halogen Tridentates, Se—Se Tetradentates or Se—Se or polarizing or water-insolubilizing groups Hexadentates) attached. Se Valence Stabilizer #13: Macrocyclic ligands containing at least one 5- Four-, or Six-Membered Macrocyclics, membered heterocyclic ring. These Macrobicyclics, and Macropolycyclics heterocyclic rings provide selenium binding (including Catapinands, Cryptands, sites to valence stabilize the central metal ion. Cyclidenes, and Sepulchrates) wherein all Other selenol or selenoether binding sites can Binding Sites are composed of Selenium also be included in the macrocyclic ligand, so and are contained in a Combination of 5- long as the total number of binding sites is four Membered Heterocyclic Rings and Selenol or six. Can include other hydrocarbon/ring or Selenoether Groups (Se—Se Tridentates, systems bound to this macrocyclic ligand, but Se—Se Tetradentates, or Se—Se they do not coordinate with the stabilized, high Hexadentates) valence metal ion. This ligand and/or attached, uncoordinating hydrocarbon/rings may or may not have halogen or polarizing or water- insolubilizing groups attached. Se Valence Stabilizer #14: Macrocyclic ligands containing a total of four or Four-, or Six-Membered Macrocyclics, six six-membered heterocyclic rings containing Macrobicyclics, and Macropolycyclics selenium binding sites. Can include other (including Catapinands, Cryptands, hydrocarbon/ring systems bound to this Cyclidenes, and Sepulchrates) wherein all macrocyclic ligand, but they do not coordinate Binding Sites are composed of Selenium with the stabilized, high valence metal ion. This and are contained in Component 6- ligand and/or attached, uncoordinating Membered Heterocyclic Rings (Se—Se hydrocarbon/rings may or may not have halogen Tridentates, Se—Se Tetradentates, or Se—Se or polarizing or water-insolubilizing groups Hexadentates) attached. Se Valence Stabilizer #15: Macrocyclic ligands containing at least one 6- Four-, or Six-Membered Macrocyclics, membered heterocyclic ring. These Macrobicyclics, and Macropolycyclics heterocyclic rings provide selenium binding (including Catapinands, Cryptands, sites to valence stabilize the central metal ion. Cyclidenes, and Sepulchrates) wherein all Other selenol or selenoether binding sites can Binding Sites are composed of Selenium also be included in the macrocyclic ligand, so and are contained in a Combination of 6- long as the total number of binding sites is four Membered Heterocyclic Rings and Selenol or six. Can include other hydrocarbon/ring or Selenoether Groups (Se—Se Tridentates, systems bound to this macrocylic ligand, but Se—Se Tetradentates, or Se—Se they do not coordinate with the stabilized, high Hexadentates) valence metal ion. This ligand and/or attached, uncoordinating hydrocarbon/rings may or may not have halogen or polarizing or water- insolubilizing groups attached. Se Valence Stabilizer #16: R—C(═Se)—CR′R′—C(═Se)—R″′where R, R′, R″, 1,3-Diselenoketones (Diseleno-beta- and R″′ represent H, NH2, or any organic ketonates), 1,3,5-Triselenoketones, Bis(1,3- functional group wherein the number of carbon Diselenoketones), and Poly( 1,3- atoms ranges from 0 to 40, optionally having Diselenoketones) (S—S Bidentates, S—S halogen or polarizing or water- Tridentates, S—S Tetradentates) insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. Se Valence Stabilizer #17: RR′—C═C(—Se)(—Se), where R and R′represent 1,1-Diselenolates, Bis(1,1-diselenolates), H, NH2 or any organic functional group wherein and Poly(1,1-diselenolates) (Se—Se the number of carbon atoms ranges from 0 to Bidentates and Se—Se Tetradentates) 40, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. Se Valence Stabilizer #18: RR′N+═C(SeH)(SeH), where R and R′ Diselenocarbamates, represent H, OH, SH, OR″(R″═C1—C30 alkyl or Bis(diselenocarbamates), and aryl), SR″ (R″═C1—C30 alkyl or aryl), NH2 or Poly(diselenocarbamates) (including N- any organic functional group wherein the hydroxydiselenocarbamates and N— number of carbon atoms ranges from 0 to 40, mercaptodiselenocarbamates) (Se—Se optionally having halogen or polarizing or Bidentates, Se—Se Tridentates, and Se—Se water-insolubilizing/solubilizing groups Tetradentates) attached. Ligand can also contain nonbinding N, O, S, or P atoms. Se Valence Stabilizer #19: (O═)P(—Se—R)(—Se—R′)(—Se—R″) or (Se═)P(—Se— Triselenophosphoric Acids R)(—Se—R′)(—O—R″), where R, R′, and R″ (Phosphorotriselenoic Acids), represent H, NH2 or any organic functional Bis(triselenophosphoric acids), group wherein the number of carbon atoms Poly(triselenophosphoric acids), and ranges from 0 to 40, optionally having halogen derivatives thereof (Se—Se Bidentates, Se—Se or polarizing or water- Tridentates, Se—Se Tetradentates) insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. Se Valence Stabilizer #20: (O═)P(—Se—R)(—Se—R′)(—O—R″) or (Se═)P(—Se— Diselenophosphoric Acids R)(—O—R′)(—O—R″), where R, R′, and R″ (Phosphorodiselenoic Acids), represent H, NH2 or any organic functional Bis(diselenophosphoric acids), group wherein the number of carbon atoms Poly(diselenophosphoric acids), and ranges from 0 to 40, optionally having halogen derivatives thereof (Se—Se Bidentates, Se—Se or polarizing or water- Tridentates, Se—Se Tetradentates) insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. Se Valence Stabilizer #21: (Se═)P(—Se—R)(—Se—R′)(—Se—R″), where R, R′, Tetraselenophosphoric Acids and R″ represent H, NH2 or any organic (Phosphorotetraselenoic Acids), functional group wherein the number of carbon Bis(tetraselenophosphoric acids), atoms ranges from 0 to 40, optionally having Poly(tetraselenophosphoric acids), and halogen or polarizing or water- derivatives thereof (Se—Se Bidentates, Se—Se insolubilizing/solubilizing groups attached. Tridentates, Se—Se Tetradentates) Ligand can also contain nonbinding N, O, S, or P atoms. Se Valence Stabilizer #22: R—Se—C(═Se)—O—R′ or R—Se—C(═O)—Se—R′ for Diselenocarbonates, Triselenocarbonates, diselenocarbonates, and R—Se—C(═Se)—Se—R′ for Bis(diselenocarbonates), and triselenocarbonates, where R, and R′ represent Bis(triselenocarbonates), (Se—Se Bidentates H, NH2 or any organic functional group wherein and Se—Se Tetradentates) the number of carbon atoms ranges from 0 to 40, optionally having halogen or polarizing or water-insolubilizing/solubilizing groups attached. Ligand can also contain nonbinding N, O, S, or P atoms. Se Valence Stabilizer #23: Selenocyanates bound directly to the high Selenocyanates (Se Monodentates) valence metal ion. Se Valence Stabilizer #24: Selenolates (HSe—R, HSe—R—SeH, etc.), where R Selenolates (Se Monodentates) and R′represent H or any organic functional group wherein the number of carbon atoms ranges from 0 to 35, optionally having halogen or polarizing or water- insolubilizing/solubilizing groups attached. Miscellaneous Valence Stabilizer #1: Dialkenes or bicyclic or tricyclic hydrocarbons Diene or bicyclic or tricyclic hydrocarbon bound directly to the high valence metal ion. ligands Miscellaneous Valence Stabilizer #2: Cyanide and cyanate and related ligands bound Cyanide and related ligands directly to the high valence metal ion. Miscellaneous Valence Stabilizer #3: Carbonyl (—CO) ligands bound directly to the Carbonyl ligands high valence metal ion. Miscellaneous Valence Stabilizer #4: Halogen (X) atoms bound directly to the high Halogen ligands valence metal ion.
[0358] N Valence Stabilizer #1a: Examples of five-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen (usually amine or imine groups) and are not contained in component heterocyclic rings (N—N Tridentates or N—N Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: pentaazacyclodecane ([10]aneN5); pentaazacycloundecane ([11]aneN5); pentaazacyclododecane ([12]aneN5); pentaazacyclotridecane ([13]aneN5); pentazaacyclotetradecane ([14]aneN5); pentaazacyclopentadecane ([15]aneN5); pentaazacyclodecatriene ([10]trieneN5); pentaazacycloundecatriene ([11]trieneN5); pentaazacyclododecatriene ([12 trieneN5); pentaazacyclotridecatriene ([13]trieneN5); pentazaacyclotetradecatriene ([14]trieneN5); and pentaazacyclopentadecatriene ([15]trieneN5).
[0359] N Valence Stabilizer #1b: Examples of seven-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen (usually amine or imine groups) and are not contained in component heterocyclic rings (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: heptaazacyclotetradecane ([14]aneN7); heptaazacyclopentadecane ([15]aneN7); heptaazacyclohexadecanc ([16]aneN7); heptaazacycloheptadecane ([17]aneN7); heptaazacyclooctadecane ([18]aneN7); heptaazacyclononadecane ([19]aneN7); heptaazacycloeicosane ([20]aneN7); heptaazacycloheneicosane ([21] aneN7); heptaazacyclotetradecatriene ([14]trieneN7); heptaazacyclopentadecatriene ([15]trieneN7); heptaazacyclohexadecatriene ([16]trieneN7); heptaazacycloheptadecatriene ([17]trieneN7); heptaazacyclooctadecatriene ([18]trieneN7); heptaazacyclononadecatriene ([19]trieneN7); heptaazacycloeicosatriene ([20]trieneN7); and heptaazacycloheneicosatriene ([21]trieneN7).
[0360] N Valence Stabilizer #1c: Examples of nine-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen (usually amine or imine groups) and are not contained in component heterocyclic rings (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for include, but are not limited to: nonaazacyclooctadecane ([18]aneN9); nonaazacyclononadecane ([19]aneN9); nonaazacycloeicosane ([20]aneN9); nonaazacycloheneicosane ([21]aneN9); nonaazacyclodocosane ([22]aneN9); nonaazacyclotricosane ([23]aneN9); nonaazacyclotetracosane ([24]aneN9); nonaazacyclopentacosane ([25]aneN9); nonaazacyclohexacosane ([26]aneN9); nonaazacycloheptacosane ([27]aneN9); nonaazacyclooctadecatetradiene ([18]tetradieneN9); nonaazacyclononadecatetradiene ([19]tetradieneN9); nonaazacycloeicosatetradiene ([20]tetradieneN9); nonaazacycloheneicosatetradiene ([21]tetradieneN9); nonaazacyclodocosatetradiene ([22]tetradieneN9); nonaazacyclotricosatetradiene ([23]tetradieneN9); nonaazacyclotetracosatetradiene ([24]tetradieneN9); nonaazacyclopentacosatetradiene ([25]tetradieneN9); nonaazacyclohexacosatetradiene ([26]tetradieneN9); and nonaazacycloheptacosatetradiene ([27]tetradieneN9).
[0361] N Valence Stabilizer #2a: Examples of five-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all five binding sites are composed of nitrogen and are contained in component 5-membered heterocyclic rings (N—N Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: pentaphyrins (pentapyrroles); sapphyrins; smaragdyrins; pentaoxazoles; pentaisooxazoles; pentathiazoles; pentaisothiazoles; pentaazaphospholes; pentaimidazoles; pentapyrazoles; pentaoxadiazoles; pentathiadiazoles; pentadiazaphospholes; pentatriazoles; pentaoxatriazoles; and pentathiatriazoles.
[0362] N Valence Stabilizer #2b: Examples of seven-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all seven binding sites are composed of nitrogen and are contained in component 5-membered heterocyclic rings (N—N Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: heptaphyrins (heptapyrroles); heptaoxazoles; heptaisooxazoles; heptathiazoles; heptaisothiazoles; heptaazaphospholes; heptaimidazoles; heptapyrazoles; heptaoxadiazoles; heptathiadiazoles; heptadiazaphospholes; heptatriazoles; heptaoxatriazoles; and heptathiatriazoles.
[0363] N Valence Stabilizer #3a: Examples of five-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all five binding sites are composed of nitrogen and are contained in a combination of 5-membered heterocyclic rings and amine or imine groups (N—N Tridentates or N—N Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: superphthalocyanine; supernaphthalocyanine; diazapentaphyrins; tetraazapentaphyrins; pentaazapentaphyrins; diazapentapyrazoles; tetraazapentapyrazoles; pentaazapentapyrazoles; diazapentaimidazoles; tetraazapentaimidazoles; and pentaazapentaimidazoles.
[0364] N Valence Stabilizer #3b: Examples of seven-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all seven binding sites are composed of nitrogen and are contained in a combination of 5-membered heterocyclic rings and amine or imine groups (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diazabeptaphyrins; tetraazaheptaphyrins; hexaazaheptaphyrins; diazaheptapyrazoles; tetraazaheptapyrazoles; hexaazaheptapyrazoles; diazaheptaimidazoles; tetraazaheptaimidazoles; and hexaazaheptaimidazoles.
[0365] N Valence Stabilizer #3c: Examples of nine-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all nine binding sites are composed of nitrogen and are contained in a combination of 5-membered heterocyclic rings and amine or imine groups (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include,-but are not limited to: diazanonaphyrins; tetraazanonaphyrins; hexaazanonaphyrins; diazanonapyrazoles; tetraazanonapyrazoles; hexaazanonapyrazoles; diazanonaimidazoles; tetraazanonaimidazoles; and hexaazanonaimidazoles.
[0366] N Valence Stabilizer #4a: Examples of five-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all five binding sites are composed of nitrogen and are contained in component 6-membered heterocyclic rings (N—N Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: cyclopentapyridines; cyclopentaoxazines; cyclopentathiazines; cyclopentaphosphorins; cyclopentaquinolines; cyclopentapyrazines; cyclopentapyridazines; cyclopentapyrimidines; cyclopentaoxadiazines; cyclopentathiadiazines; cyclopentadiazaphosphorins cyclopentaquinoxalines; cyclopentatriazines; cyclopentathiatriazines; and cyclopentaoxatriazines.
[0367] N Valence Stabilizer #4b: Examples of seven-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all seven binding sites are composed of nitrogen and are contained in component 6-membered heterocyclic rings (N—N Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: cycloheptapyridines; cycloheptaoxazines; cycloheptathiazines; cycloheptaphosphorins; cycloheptaquinolines; cycloheptapyrazines; cycloheptapyridazines; cycloheptapyrimidines; cycloheptaoxadiazines; cycloheptathiadiazines; cycloheptadiazaphosphorins cycloheptaquinoxalines; cycloheptatriazines; cycloheptathiatriazines; and cycloheptaoxatriazines.
[0368] N Valence Stabilizer #5a: Examples of five-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all five binding sites are composed of nitrogen and are contained in a combination of 6-membered heterocyclic rings and amine or imine groups (N—N Tridentates or N—N Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diazacyclopentapyridines; tetraazacyclopentapyridines; diazacyclopentaquinolines; tetraazacyclopentaquinolines; diazacyclopentapyrazines; tetraazacyclopentapyrazines; diazacyclopentapyridazines; tetraazacyclopentapyridazines; diazacyclopentapyrimidines; tetraazacyclopentapyrimidines; diazacyclopentatriazines; and tetraazacyclopentatriazines.
[0369] N Valence Stabilizer #5b: Examples of seven-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all seven binding sites are composed of nitrogen and are contained in a combination of 6-membered heterocyclic rings and amine or imine groups (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diazacycloheptapyridines; tetraazacycloheptapyridines; diazacycloheptaquinolines; tetraazacycloheptaquinolines; diazacycloheptapyrazines; tetraazacycloheptapyrazines; diazacycloheptapyridazines; tetraazacycloheptapyridazines; diazacycloheptapyrimidines; tetraazacycloheptapyrimidines; diazacycloheptatriazines; and tetraazacycloheptatriazines.
[0370] N Valence Stabilizer #5c: Examples of nine-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all nine binding sites are composed of nitrogen and are contained in a combination of 6-membered heterocyclic rings and amine or imine groups (N—N Tridentates, N—N Tetradentates, or N—N Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diazacyclononapyridines; tetraazacyclononapyridines; diazacyclononaquinolines; tetraazacyclononaquinolines; diazacyclononapyrazines; tetraazacyclononapyrazines; diazacyclononapyridazines; tetraazacyclononapyridazines; diazacyclononapyrimidines; tetraazacyclononapyrimidines; diazacyclononatriazines; and tetraazacyclononatriazines.
[0371] N Valence Stabilizer #6: Examples of silylamines and silazanes (N Monodentates, N—N Bidentates, N—N Tridentates, N—N Tetradentates, and N—N Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: trisilylamine; N-methyldisilazane (disilylmethylamine); N,N-dimethylsilylamine; (silyldimethylamine); tris(trimethylsilyl)amine; triethylsilylamine (triethylaminosilane) (triethylsilazane); N-ethyltriethylsilylamine (triethyl-N-ethylaminosilane); di-tert-butylsilanediamine (di-tert-butyldiaminosilane); bis(methylamino)diethylsilane; tris(dimethylamino)ethylsilane; hexamethyldisilazane; N-methylhexaphenyldisilazane; hexamethylcyclotrisilazane; and octaphenylcyclotetrasilazane. [Note: Silylamines and silazanes are notably weaker ligands than their carbonaceous derivatives, although replacement of one or two SiR3 groups with CR3 will enhance the donor power of the ligand. Thus, N(CR3)2(SiR3) is a better ligand than N(CR3)(SiR3)2, etc.]
[0372] N Valence Stabilizer #7: Examples of guanidines, diguanidines, and polyguanidines (N—N bidentates, N—N tridentates, N—N tetradentates, and N—N hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: guanidine; methylguanidine; ethylguanidine; isopropylguanidine; butylguanidine; benzylguanidine; phenylguanidine; tolylguanidine; naphthylguanidine; cyclohexylguanidine; norbornylguanidine; adamantylguanidine; dimethylguanidine; diethylguanidine; diisopropylguanidine; dibutylguanidine; dibenzylguanidine; diphenylguanidine; ditolylguanidine; dinaphthylguanidine; dicyclohexylguanidine; dinorbornylguanidine; diadamantylguanidine; ethylenediguanidine; propylenediguanidine; tetramethylenediguanidine; pentamethylenediguanidine; hexamethylenediguanidine; heptamethylenediguanidine; octamethylenediguanidine; phenylenediguanidine; piperazinediguanidine; oxalyldiguanidine; malonyldiguanidine; succinyldiguanidine; glutaryldiguanidine; adipyldiguanidine; pimelyldiguanidine; suberyldiguanidine; phthalyldiguanidine; benzimidazoleguanidine; aminoguanidine; nitroaminoguanidine; dicyandiamide (cyanoguanidine); dodecylguanidine; and nitrovin.
[0373] N Valence Stabilizer #8: Examples of phosphonitrile amides and bis(phosphonitrile amides) (N—N Bidentates and N—N Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: phosphononitrile amide; N-phenylphosphonitrile amide; N-benzylphosphonitrile amide; N-cyclohexylphosphonitrile amide; N-norbornylphosphonitrile amide; N,N′-diphenylphosphonitrile amide; N,N′-dibenzylphosphonitrile amide; N,N′-dicyclohexylphosphonitrile amide; and N,N′-dinorbornylphosphonitrile amide. [Note: The phosphite (P+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]
[0374] N Valence Stabilizer #9: Examples of phosphonimidic diamides, bis(phosphonimidic diamides), and poly(phosphonimidic diamides) (N—N bidentates and N—N tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: phosphonimidic diamide; N-benzylphosphonimidic diamide; N-phenylphosphonimidic diamide; N-cyclohexylphosphonimidic diamide; N-norbornylphosphonimidic diamide; N,N-dibenzylphosphonimidic diamide; N,N-diphenylphosphonimidic diamide; N,N-dicyclohexylphosphonimidic diamide; and N,N-dinorbornylphosphonimidic diamide. [Note: The phosphite (P+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]
[0375] N Valence Stabilizer #10: Examples of phosphonamidimidic acid, phosphonamidimidothioic acid, bis(phosphonamidimidic acid), bis(phosphonamidimidothioic acid), poly(phosphonamidimidic acid), poly(phosphonamidimidothioic acid), and derivatives thereof (N—N Bidentates, and N—N Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: phosphonamidimidic acid, phosphonamidimidothioic acid; O-phenylphosphonamidimidic acid; O-benzylphosphonamidimidic acid; O-cyclohexylphosphonamidimidic acid; O-orbornylphosphonamidimidic acid; S-phenylphosphonamidimidothioic acid; S-enzylphosphonamidimidothioic acid; S-cyclohexylphosphonamidimidothioic acid; and S-orbornylphosphonamidimidothioic acid. [Note: The phosphite (P+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]
[0376] Valence Stabilizer #11: Examples of pyridinaldimines, bis(pyridinaldimines), and poly(pyridinaldimines) (N—N Bidentates, N—N Tridentates, and N—N Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: pyridylideneaniline [N-(pyridylmethylene)benzenamine]; and (2-pyridyl)benzylideneaniline.
[0377] N Valence Stabilizer #12: Examples of hydrazones, bis(hydrazones), and poly(hydrazones) (N Monodentates, N—N Bidentates, N—N Tridentates, and N—N Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: acetaldehyde hydrazone; acetaldehyde phenylhydrazone; acetone hydrazone; acetone phenylhydrazone; pinacolone hydrazone; pinacolone phenylhydrazone; benzaldehyde hydrazone; benzaldehyde phenylhydrazone; naphthaldehyde hydrazone; naphthaldehyde phenylhydrazone; norbornanone hydrazone; norbornanone phenylhydrazone; camphor hydrazone; camphor phenylhydrazone; nopinone hydrazone; nopinone phenylhydrazine; 2-pyridinaldehyde hydrazone; 2-pyridinealdehyde phenylhydrazone; salicylaldehyde hydrazone; salicylaldehyde phenylhydrazone; quinolinaldehyde hydrazone; quinolinaldehyde phenylhydrazone; isatin dihydrazone; isatin di(phenylhydrazone); camphorquinone dihydrazone; camphorquinone di(phenylhydrazone); and 2-hydrazinobenzimidazole hydrazone.
[0378] N Valence Stabilizer #13: Examples of azo compounds without chelate substitution at the ortho- (for aryl) or alpha- or beta- (for alkyl) positions, bis(azo compounds), or poly(azo compounds) (N Monodentates, N—N Bidentates, or N—N Tridentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: azobenzene (diphenyldiazene); p-diaminoazobenzene; p-dimethylaminoazobenzene (butter yellow); methyl orange; Fast Garnet GBC (4′-amino-2,3′-dimethylazobenzene)[Note: non-bonding methyl group in the o-position.]; and Alizarin Yellow R. [Note: Azo compounds without chelate substitution at the ortho- (for aryl) or beta- (for alkyl) positions tend to stabilize lower oxidation states in metal ions.]
[0379] N Valence Stabilizer #14: Examples of formazans, bis(formazans), and poly(formazans) without ortho- hydroxy, carboxy, thiol, mercapto, amino, or hydrazido substitution (N—N Bidentates, N—N Tetradentates, and N—N Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 1,3,5-triphenylformazan; and 1,3,5-naphthylformazan.
[0380] N Valence Stabilizer #15: Examples of hydramides (N—N Bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: hydrobenzamide; hydronaphthamide; and hydrosalicylamide.
[0381] N Valence Stabilizer #16: Examples of azines (including ketazines), bis(azines), and poly(azines) without ortho-hydroxy, carboxy, thiol, mercapto, amino, or hydrazido substitution (N—N Bidentates, N—N Tetradentates, and N—N Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: benzalazine; napbthalazine; cyclohexanonazine; and norbornonazine.
[0382] N Valence Stabilizer #17: Examples of Schiff Bases with one Imine (C═N) Group and without ortho- (for aryl constituents) or alpha- or beta- (for alkyl constituents) hydroxy, carboxy, carbonyl, thiol, mercapto, thiocarbonyl, amino, imino, oximo, diazeno, or hydrazido substitution (N Monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N-(Benzaldehydo)isopropylamine; N-(Naphthaldehydo)isopropylamine; N-(Acetophenono)isopropyl amine; N-(Propiophenono)isopropylamine; N-(Benzaldehydo)cyclohexylamine; N-(Naphthaldehydo)cyclohexylamine; N-(Acetophenono)cyclohexylamine; N-(Propiophenono)cyclohexylamine; N-(Benzaldehydo)aniline (BAAN); N-(Naphthaldehydo)aniline; N-(Acetophenono)aniline; N-(Propiophenono)aniline; N-(Benzaldehydo)aminonorbornane; N-(Naphthaldehydo)aminonorbornane; N-(Acetophenono)aminonorbornane; N-(Propiophenono)aminonorbornane; (Vanillino)anisidine; (Cinnamaldehydo)anisidine; N-(o-carboxycinnamaldehydo)aniline; N-(cinnamaldehydo)aniline; N-(cinnamaldehydo)m- or p-anisidine; and N-(o-carboxycinnamaldehydo)m- or p-anisidine.
[0383] N Valence Stabilizer #18: Examples of isocyanide and cyanamide and related ligands (N Monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: isocyanate (—NCO); isothiocyanate (—NCS); isoselenocyanate (—NCSe); and cyanamide (—NCN). [Note: the nitrogen atom is directly complexed to the high valence metal ion.]
[0384] N Valence Stabilizer #19: Examples of nitrosyls and nitrites and related ligands (N Monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: nitrosyl (—NO); thionitrosyl (—NS); nitrite (—NO2); thionitrite (sulfinylamide)(thiazate)(—NSO); nitrosamine (═NN═O); thionitrosamine (NN═S); nitramine (═NNO2); and thionitramine (═NNS2) ligands.
[0385] N Valence Stabilizer #20: Examples of nitriles, dinitriles, and polynitriles (N Monodentates, N—N Bidentates, N—N Tridentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: benzonitrile; naphthonitrile; cyanonaphthalene; cyclohexyl nitrile; cyanopyridine; cyanopurine; cyanophenol; cyanothiophenol; adamantane nitrile; norbornyl nitrile; cinnamonitrile; dicyanobenzene; dicyanobutene; dicyanoimidazole; dicyanopyridine; cyanotolunitrile; tetracyanoethylene (TCNE); tetracyanoquinodimethane (TCNQ); diethylaminopropionitrile (deapn), and polyacrylonitriles.
[0386] N Valence Stabilizer #21: Examples of azide ligands (N monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: azide (—N3) ions; methyl azide; ethyl azide; phenyl azide; diphenyltriazene; and phenyl sulfonyl azide.
[0387] S Valence Stabilizer #1: Examples of monothioethers (S monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: hydrogen sulfide, dimethyl sulfide, diethyl sulfide, dioctyl sulfide, diphenyl sulfide, dicyclohexyl sulfide, tetramethylene sulfide (tetrahydrothiophene, tht), trimethylene sulfide, dimethylene sulfide (ethylene sulfide), pentamethylene sulfide, 1,4-thioxane, oxathiolane, cyclohexene sulfide, cyclooctene sulfide, benzotetrahydrothiophene, dibenzothiophene, naphthotetrahydrothiophene, and thiabicycloheptane.
[0388] S Valence Stabilizer #2: Examples of disulfides (S monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: methyl disulfide, ethyl disulfide, phenyl disulfide, nitrophenide, and 1,2-dithiacyclohexane.
[0389] S Valence Stabilizer #3: Examples of dithioethers (S monodentates or S—S bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 1,3-dithiane, 1,4-dithiane, benzodithiane, dibenzodithiane, naphthodithiane, 2,5-dithiahexane (dth); 3,6-dithiaoctane (dto); 2,5-dimethyl-3,6-dithiaoctane; 3,7-dithianonane; 2,6-dithiaheptane; 1,6-diphenyl-2,5-dithiahexane; 1,4-dipbenyl-1,4-dithiabutane; 1,3-dithiolane; 1,4-dithiane (1,4-dithiacyclohexane); 1,4-dithiacycloheptane (dtch); 1,5-dithiacyclooctane (dtco); o-phenylenebis(2-thiapropane); o-phenylenebis(2-thiabutane); 2,2′-(thiamethyl)biphenyl, and 2,2′-(thiaethyl)biphenyl.
[0390] S Valence Stabilizer #4: Examples of trithioethers (S monodentates, S—S bidentates, or S—S tridentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 1,3,5-trithiane; 1,3,5-tris(methylthia)cyclohexane; 1,3,5-tris(ethylthia)cyclohexane; 1,3,5-tris(phenylthia)cyclohexane; 2,5,8-trithianonane; 3,6,9-trithiaundecane; and 2,6,10-trithiaundecane.
[0391] S Valence Stabilizer #5: Examples of tetrathioetbers (S monodentates, S—S bidentates, S—S tridentates, or S—S tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 1,4,10,13-tetrathiatridecane; 2,6,10,14-tetrathiapentadecane; 2,5,8,11-tetrathiadodecane; 2,5,9,12-ttetrathiatridecane; 2,6,9,13-tetrathiatetradecane; 1,4-(o-thiomethyl)phenyl-1,4-dithiabutane; 1,5-(o-thiomethyl)phenyl-1,5-dithiapentane; 1,6-(o-thiomethyl)phenyl-1,6-dithiahexane; 1,4-(o-thiomethyl)phenyl-1,4-dithiabut-2-ene; and polythioethers.
[0392] S Valence Stabilizer #6: Examples of hexathioethers (S monodentates, S—S bidentates, S—S tridentates, S—S tetradentates, or S—S hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: tri(2-((o-thiomethyl)phenyl)ethyl)amine; and tri((o-thiomethyl)phenyl)methylamine.
[0393] S Valence Stabilizer #7a: Examples of 5-membered heterocyclic rings containing one sulfur atom (S monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dihydrothiophene, thiophene, thiazole, thiapyrroline, thiaphospholene, thiaphosphole, oxathiole, thiadiazole, thiatriazole, benzodihydrothiophene, benzothiophene, benzothiazole, benzothiaphosphole, dibenzothiophene, and naphthothiophene.
[0394] S Valence Stabilizer #7b: Examples of 5-membered heterocyclic rings containing two sulfur atoms (S monodentates or S—S bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiole, benzodithiole, and naphthodithiole.
[0395] S Valence Stabilizer #8a: Examples of 6-membered heterocyclic rings containing one sulfur atom (S monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dihydrothiopyran, thiopyran, thiazine, thiadiazine, thiaphosphorin, thiadiphosphorin, oxathiin, benzothiopyran, dibenzothiopyran, and naphthothiopyran.
[0396] S Valence Stabilizer #8b: Examples of 6-membered heterocyclic rings containing two sulfur atoms (S monodentates or S—S bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dihydrodithiin, dithiin, benzodithiin, dibenzodithiin (thianthrene), and naphthodithiin.
[0397] S Valence Stabilizer #9a: Examples of 5-membered heterocyclic rings containing one sulfur atom and having at least one additional sulfur atom binding site not contained in a ring (S Monodentates, S—S Bidentates, S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2,5-dimercapto-2,5-dihydrothiophene; 2,5-bis(thiomethyl)-2,5-dihydrothiophene; 2,5-bis(2-thiophenyl)-2,5-dihydrothiophene; 2,5-dimercaptothiophene; 2,5-bis(thiomethyl)thiophene; 2,5-bis(2-thiophenyl)thiophene; 2,5-dimercatothiazole; 2,5-bis(thiomethyl)thiazole; 2,5-bis(2-thiophenyl)thiazole; 2,5-dimercapto-1,3,4-thiadiazole [bismuththiol]; 2-mercaptothianaphthene; 7-(thiomethyl)thianaphthene; 1,8-dimercaptodibenzothiophene; 2-mercaptobenzothiazole; 2-mercapro-1,3,4-thiadiazole; 2-amino-5-mercapto-1,3,4-thiadiazole; 2,5-bis(alkylthio)-1,3,4-thiadiazole; and 7-(thiomethyl)benzothiazole.
[0398] S Valence Stabilizer #9b: Examples of 5-membered heterocyclic rings containing two sulfur atoms and having at least one additional sulfur atom binding site not contained in a ring (S Monodentates, S—S Bidentates, S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-mercapto-1,3-dithiole; 2-(dimercaptomethyl)-1,3-dithiole; 4,5-dimercapto-1,3-dithiole; 4,5-bis(2-thiophenyl)-1,3-dithiole; 2-mercaptobenzodithiole; and 7-mercaptobenzodithiole.
[0399] S Valence Stabilizer #10a: Examples of 6-membered heterocyclic rings containing one sulfur atom and having at least one additional sulfur atom binding site not contained in a ring (S Monodentates, S—S Bidentates, S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2,6-dimercapto-2,5-dihydrothiopyran; 2,6-bis(thiomethyl)-2,5-dihydrothiopyran; 2,6-bis(2-thiophenyl)-2,5-dihydrothiopyran; 2,6-dimercaptothiopyran; 2,6-bis(thiomethyl)thiopyran; 2,6-bis(2-thiophenyl)thiopyran; 2,6-dimercaptothiazine; 2,6-bis(thiomethyl)thiazine; 2,6-bis(2-thiophenyl)thiazine; 2,6-dimercapto-1,3,5-thiadiazine; 2-mercapto-1-benzothiopyran; 8-mercapto-1-benzothiopyran; and 1,9-dimercaptodibenzothiopyran.
[0400] S Valence Stabilizer #10b: Examples of 6-membered heterocyclic rings containing two sulfur atoms and having at least one additional sulfur atom binding site not contained in a ring (S Monodentates, S—S Bidentates, S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-mercapto-1,4-dithiin; 2,6-dimercapto-1,4-dithiin; 2,6-bis(2-thiophenyl)-1,4-dithiin; 2,3-dimercapto-1,4-benzodithiin; 5,8-dimercapto-1,4-benzodithiin; 1,8-dimercaptothianthrene; and 1,4,5,8-tetramercaptothianthrene.
[0401] S Valence Stabilizer #11a: Examples of 5-membered heterocyclic rings containing one sulfur atom and having at least one additional sulfur atom binding site contained in a ring (S Monodentates, S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2,2′-bi-2,5-dihydrothiophene; 2,2′,2″-tri-2,5-dihydrothiophene; 2,2′-bithiophene; 2,2′,2″-trithiophene; 2,2′-bithiazole; 5,5′-bithiazole; 2,2′-bioxathiole; 2,2′-bi-1,3,4-thiadiazole; 2,2′-bithianaphthene; 2,2′-bibenzothiazole; 1,1′-bis(dibenzothiophene); and polythiophenes.
[0402] S Valence Stabilizer #11b: Examples of 5-membered heterocyclic rings containing two sulfur atoms and having at least one additional sulfur atom binding site contained in a ring (S Monodentates, S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2,2′-bi-1,3-dithiole; 4,4′-bi-1,3-dithiole; 7,7′-bi-1,2-benzodithiole; 3,3′-bi-1,2-benzodithiole; and tetrathiofulvalene.
[0403] S Valence Stabilizer #12a: Examples of 6-membered heterocyclic rings containing one sulfur atom and having at least one additional sulfur atom binding site contained in a ring (S Monodentates, S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2,2′-bi-2,5-dihydrothiopyran; 2,2′,2″-tri-2,5-dihydrothiopyran; 2,2′-bithiopyran; 2,2′,2″-trithiopyran; 2,2′-bi-1,4-thiazine; 2,2′-bi-1,3,5-thiadiazine; 2,2′-bi-1-benzothiopyran; and 1,1′-bis(dibenzothiopyran)
[0404] S Valence Stabilizer #12b: Examples of 6-membered heterocyclic rings containing two sulfur atoms and having at least one additional sulfur atom binding site contained in a ring (S Monodentates, S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2,2′-bi-1,4-dithiin; 2,2′-bi-1,3-dithiin; 5,5′-bi-1,4-benzodithiin; 2,2′-bi-1,3-benzodithiin; and 1,1′-bithianthrene.
[0405] S Valence Stabilizer #13a: Examples of two-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein both binding sites are composed of sulfur (usually thiol or thioether groups) and are not contained in component heterocyclic rings (S—S Bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiacyclobutane ([4]aneS2); dithiacyclopentane ([5]aneS2); dithiacyclohexane ([6]aneS2); dithiacycloheptane ([7]aneS2); dithiacyclooctane ([8]aneS2); dithiacyclobutene ([4]cneS2); dithiacyclopentene ([5]eneS2); dithiacyclohexene ([6]eneS2); dithiacycloheptene ([7]eneS2); dithiacyclooctene ([8]eneS2); dithiacyclobutadiene ([4]dieneS2); dithiacyclopentadiene ([5]dieneS2); dithiacyclohexadiene ([6]dieneS2); dithiacycloheptadiene ([7]dieneS2); and dithiacyclooctadiene ([8]dieneS2).
[0406] S Valence Stabilizer #13b: Examples of three-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of sulfur (usually thiol or thioether groups) and are not contained in component heterocyclic rings (S—S Tridentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: trithiacyclohexane ([6]aneS3); trithiacycloheptane ([7]aneS3); trithiacyclooctane ([8]aneS3); trithiacyclononane ([9]aneS3); trithiacyclodecane ([10]aneS3); trithiacycloundecane ([11]aneS3); trithiacyclododecane ([12]aneS3); trithiacyclohexene ([6]eneS3); trithiacycloheptene ([7]eneS3); trithiacyclooctene ([8]eneS3); trithiacyclononene ([9]eneS3); trithiacyclodecene ([10]eneS3); trithiacycloundecene ([11]eneS3); trithiacyclododecene ([12]eneS3); trithiacyclohexatriene ([6]trieneS3); trithiacycloheptatriene ([7]trieneS3); trithiacyclooctatriene ([8]trieneS3); trithiacyclononatriene ([9]trieneS3); trithiacyclodecatriene ([10]trieneS3); trithiacycloundecatriene ([11]trieneS3); and trithiacyclododecatriene ([12]trieneS3).
[0407] S Valence Stabilizer #13c: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of sulfur (usually thiol or thioether groups) and are not contained in component heterocyclic rings (S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: tetrathiacyclooctane ([8]aneS4); tetrathiacyclononane ([9]aneS4); tetrathiacyclodecane ([10]aneS4); tetrathiacycloundecane ([11]aneS4); tetrathiacyclododecane ([12]aneS4); tetrathiacyclotridecane ([13]aneS4); tetrathiacyclotetradecane ([14]aneS4); tetrathiacyclopentadecane ([15]aneS4); tetrathiacyclohexadecane ([16]aneS4); tetrathiacycloheptadecane ([17]aneS4); tetrathiacyclooctadecane ([18]aneS4); tetrathiacyclononadecane ([19]aneS4); tetrathiacycloeicosane ([20]aneS4); tetrathiacyclooctadiene ([8]dieneS4); tetrathiacyclononadiene ([9]dieneS4); tetrathiacyclodecadiene ([10]dieneS4); tetrathiacycloundecadiene ([11]dieneS4); tetrathiacyclododecadiene ([12]dieneS4); tetrathiacyclotridecadiene ([13]dieneS4); tetrathiacyclotetradecadiene ([14]dieneS4); tetrathiacyclopentadecadiene ([15]dieneS4); tetrathiacyclohexadecadiene ([16]dieneS4); tetrathiacycloheptadecadiene ([17]dieneS4); tetrathiacyclooctadecadiene ([18]dieneS4); tetrathiacyclononadecadiene ([19]dieneS4); tetrathiacycloeicosadiene ([20]dieneS4); tetrathiacyclooctatetradiene ([8]tetradieneS4); tetrathiacyclononatetradiene ([9]tetradieneS4); tetrathiacyclodecatetradiene ([10]tetradieneS4); tetrathiacycloundecatetradiene ([11]tetradieneS4); tetrathiacyclododecatetradiene ([12]tetradieneS4); tetrathiacyclotridecatetradiene ([13]tetradieneS4); tetrathiacyclotetradecatetradiene ([14]tetradieneS4); tetrathiacyclopentadecatetradiene ([15]tetradieneS4); tetrathiacyclohexadecatetradiene ([16]tetradieneS4); tetrathiacycloheptadecatetradiene ([17]tetradieneS4); tetrathiacyclooctadecatetradiene ([18]tetradieneS4); tetrathiacyclononadecatetradiene ([19]tetradieneS4); and tetrathiacycloeicosatetradiene ([20]tetradieneS4).
[0408] S Valence Stabilizer #13d: Examples of five-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of sulfur (usually thiol or thioether groups) and are not contained in component heterocyclic rings (S—S Tridentates or S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: pentathiacyclodecane ([10]aneS5); pentathiacycloundecane ([11]aneS5); pentathiacyclododecane ([12]aneS5); pentathiacyclotridecane ([13]aneS5); pentathiacyclotetradecane ([14]aneS5); pentathiacyclopentadecane ([15]aneS5); pentathiacyclodecatriene ([10]trieneS5); pentathiacycloundecatriene ([11]trieneS5); pentathiacyclododecatriene ([12]trieneS5); pentathiacyclotridecatriene ([13]trieneS5); pentathiacyclotetradecatriene ([14]trieneS5); and pentathiacyclopentadecatriene ([15]trieneS5).
[0409] S Valence Stabilizer #13e: Examples of six-membered macrocyclics,-macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of sulfur (usually thiol or thioether groups) and are not contained in component heterocyclic rings (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: hexathiacyclododecane ([12]aneS6); hexathiacyclotridecane ([13]aneS6); hexathiacyclotetradecane ([14]aneS6); hexathiacyclopentadecane ([15]aneS6); hexathiacyclohexadecane ([16]aneS6); hexathiacycloheptadecane ([17]aneS6); hexathiacyclooctadecane ([18]aneS6); hexathiacyclononadecane ([19]aneS6); hexathiacycloeicosane ([20]aneS6); hexathiacycloheneicosane ([21]aneS6); hexathiacyclodocosane ([22]aneS6); hexathiacyclotricosane ([23]aneS6); hexathiacyclotetracosane ([24]aneS6); hexathiacyclododecatriene ([12]trieneS6); hexathiacyclotridecatriene ([13]trieneS6); hexathiacyclotetradecatriene ([14]trieneS6); hexathiacyclopentadecatriene ([15]trieneS6); hexathiacyclohexadecatriene ([16]trieneS6); hexathiacycloheptadecatriene ([17]trieneS6); hexathiacyclooctadecatriene ([18]trieneS6); hexathiacyclononadecatriene ([19]trieneS6); hexathiacycloeicosatriene ([20]trieneS6); hexathiacycloheneicosatriene ([21]trieneS6); hexathiacyclodocosatriene ([22]trieneS6); hexathiacyclotricosatriene ([23]trieneS6); and hexathiacyclotetracosatriene ([24]trieneS6).
[0410] S Valence Stabilizer #13f: Examples of seven-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of sulfur (usually thiol or thioether groups) and are not contained in component heterocyclic rings (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: heptathiacyclotetradecane ([14]aneS7); heptathiacyclopentadecane ([15]aneS7); heptathiacyclohexadecane ([16]aneS7); heptathiacycloheptadecane ([17]aneS7); heptathiacyclooctadecane ([18]aneS7); heptathiacyclononadecane ([19]aneS7); heptathiacycloeicosane ([20]aneS7); heptathiacycloheneicosane ([21]aneS7); heptathiacyclotetradecatriene ([14]trieneS7); heptathiacyclopentadecatriene ([15]trieneS7); heptathiacyclohexadecatriene ([16]trieneS7); heptathiacycloheptadecatriene ([17]trieneS7); heptathiacyclooctadecatriene ([18]trieneS7); heptathiacyclononadecatri ene ([19]trieneS7); heptathiacycloeicosatriene ([20]trieneS7); and heptathiacycloheneicosatriene ([21]trieneS7).
[0411] S Valence Stabilizer #13g: Examples of eight-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of sulfur (usually thiol or thioether groups) and are not contained in component heterocyclic rings (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: octathiacyclohexadecane ([16]aneS8); octathiacycloheptadecane ([17]aneS8); octathiacyclooctadecane ([18]aneS8); octathiacyclononadecane ([19]aneS8); octathiacycloeicosane ([20]aneS8); octathiacycloheneicosane ([21]aneS8); octathiacyclodocosane ([22]aneS8); octathiacyclotricosane ([23]aneS8); octathiacyclotetracosane ([24]aneS8); octathiacyclohexadecatetradiene ([16]tetradieneS8); octathiacycloheptadecatetradiene ([17]tetradieneS8); octathiacyclooctadecatetradiene ([18]tetradieneS8); octathiacyclononadecatetradiene ([19]tetradieneS8); octathiacycloeicosatetradiene ([20]tetradieneS8); octathiacycloheneicosatetradiene ([21]tetradieneS8); octathiacyclodocosatetradiene ([22]tetradieneS8); octathiacyclotricosatetradiene ([23]tetradieneS8); and octathiacyclotetracosatetradiene ([24]tetradieneS8).
[0412] S Valence Stabilizer #13h: Examples of nine-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of sulfur (usually thiol or thioether groups) and are not contained in component heterocyclic rings (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: nonathiacyclooctadecane ([18]aneS9); nonathiacyclononadecane ([19]aneS9); nonathiacycloeicosane ([20]aneS9); nonathiacycloheneicosane ([21]aneS9); nonathiacyclodocosane ([22]aneS9); nonathiacyclotricosane ([23]aneS9); nonathiacyclotetracosane ([24]aneS9); nonathiacyclopentacosane ([25]aneS9); nonathiacyclohexacosane ([26]aneS9); nonathiacycloheptacosane ([27]aneS9); nonathiacyclooctadecatetradiene ([18]tetradieneS9); nonathiacyclononadecatetradiene ([19]tetradieneS9); nonathiacycloeicosatetradiene ([20]tetradieneS9); nonathiacycloheneicosatetradiene ([21]tetradieneS9); nonathiacyclodocosatetradiene ([22]tetradieneS9); nonathiacyclotricosatetradiene ([23]tetradieneS9); nonathiacyclotetracosatetradiene ([24]tetradieneS9); nonathiacyclopentacosatetradiene ([25]tetradieneS9); nonathiacyclohexacosatetradiene ([26]tetradieneS9); and nonathiacycloheptacosatetradiene ([27]tetradieneS9).
[0413] S Valence Stabilizer #13i: Examples of ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of sulfur (usually thiol or thioether groups) and are not contained in component heterocyclic rings (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: decathiacycloeicosane ([20]aneS10); decathiacycloheneicosane ([21]aneS10); decathiacyclodocosane ([22]aneS10); decathiacyclotricosane ([23]aneS10); decathiacyclotetracosane ([24]aneS10); decathiacyclopentacosane ([25]aneS10); decathiacyclohexacosane ([26]aneS10); decathiacycloheptacosane ([27]aneS10); decathiacyclooctacosane ([28]aneS10); decathiacyclononacosane ([29]aneS10); decathiacyclotriacontane ([30]aneS10); decathiacycloeicosapentadiene ([20]pentadieneS10); decathiacycloheneicosapentadiene ([21]pentadieneS10); decathiacyclodocosapentadiene ([22]pentadieneS10); decathiacyclotricosapentadiene ([23]pentadieneS10); decathiacyclotetracosapentadiene ([24]pentadieneS10); decathiacyclopentacosapentadiene ([25]pentadieneS10); decathiacyclohexacosapentadiene ([26]pentadieneS10); decathiacycloheptacosapentadiene ([27]pentadieneS10); decathiacyclooctacosapentadiene ([28]pentadieneS10); decathiacyclononacosapentadiene ([29]pentadieneS10); and decathiacyclotriacontapentadiene ([30]pentadieneS10).
[0414] S Valence Stabilizer #14a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of sulfur and are contained in component 5-membered heterocyclic rings (S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: tetrathiophenes; tetrathiazoles; tetrathiaphospholes; tetraoxathioles; tetrathiadiazoles; tetrathiatriazoles; and tetradithioles.
[0415] S Valence Stabilizer #14b: Examples of five-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all five binding sites are composed of sulfur and are contained in component 5-membered heterocyclic rings (S—S Tridentates or S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: pentathiophenes; pentathiazoles; pentathiaphospholes; pentaoxathioles; pentathiadiazoles; pentathiatriazoles; and pentadithioles.
[0416] S Valence Stabilizer #14c: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of sulfur and are contained in component 5-membered heterocyclic rings (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: hexathiophenes; hexathiazoles; hexathiaphospholes; hexaoxathioles; hexathiadiazoles; hexathiatriazol es; and hexadithioles.
[0417] S Valence Stabilizer #14d: Examples of seven-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all seven binding sites are composed of sulfur and are contained in component 5-membered heterocyclic rings (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: heptathiophenes; heptathiazoles; heptathiaphospholes; heptaoxathioles; heptathiadiazoles; heptathiatriazoles; and heptadithioles.
[0418] S Valence Stabilizer #14e: Examples of eight-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all eight binding sites are composed of sulfur and are contained in component 5-membered heterocyclic rings (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: octathiophenes; octathiazoles; octathiaphospholes; octaoxathioles; octathiadiazoles; octathiatriazoles; and octadithioles.
[0419] S Valence Stabilizer #14f: Examples of nine-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all nine binding sites are composed of sulfur and are contained in component 5-membered heterocyclic rings (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: nonathiophenes; nonathiazoles; nonathiaphospholes; nonaoxathioles; nonathiadiazoles; nonathiatriazoles; and nonadithioles.
[0420] S Valence Stabilizer #14g: Examples of ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all ten binding sites are composed of sulfur and are contained in component 5-membered heterocyclic rings (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn include, but are not limited to: decathiophenes; decathiazoles; decathiaphospholes; decaoxathioles; decathiadiazoles; decathiatriazoles; and decadithioles.
[0421] S Valence Stabilizer #15a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of sulfur and are contained in a combination of 5-membered heterocyclic rings and thiol, thioether, or thioketo groups (S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiatetrathiophenes; tetrathiatetrathiophenes; dithiatetradithioles; and tetrathiatetradithioles.
[0422] S Valence Stabilizer #15b: Examples of five-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all five binding sites are composed of sulfur and are contained in a combination of 5-membered heterocyclic rings and thiol, thioether, or thioketo groups (S—S Tridentates or S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiapentathiophenes; tetrathiapentathiophenes; dithiapentadithioles; and tetrathiapentadithioles.
[0423] S Valence Stabilizer #15c: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of sulfur and are contained in a combination of 5-membered heterocyclic rings and thiol, thioether, or thioketo groups (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiahexaathiophenes; trithiahexathiophenes; dithiahexadithioles; and trithiahexadithioles.
[0424] S Valence Stabilizer #15d: Examples of seven-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all seven binding sites are composed of sulfur and are contained in a combination of 5-membered heterocyclic rings and thiol, thioether, or thioketo groups (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “wide band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiaheptathiophenes; tetrathiaheptathiophenes; dithiaheptadithioles; and tetrathiaheptadithioles.
[0425] S Valence Stabilizer #15e: Examples of eight-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all eight binding sites are composed of sulfur and are contained in a combination of 5-membered heterocyclic rings and thiol, thioether, or thioketo groups (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiaoctathiophenes; tetrathiaoctathiophenes; dithiaoctadithioles; and tetrathiaoctadithioles.
[0426] S Valence Stabilizer #15f: Examples of nine-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all nine binding sites are composed of sulfur and are contained in a combination of 5-membered heterocyclic rings and thiol, thioether, or thioketo groups (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: trithianonathiophenes; hexathianonathiophenes; trithianonadithioles; and hexathianonadithioles.
[0427] S Valence Stabilizer #15g: Examples of ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all ten binding sites are composed of sulfur and are contained in a combination of 5-membered heterocyclic rings and thiol, thioether, or thioketo groups (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiadecathiophenes; pentathiadecathiophenes; dithiadecadithioles; and pentathiadecadithioles.
[0428] S Valence Stabilizer #16a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of sulfur and are contained in component 6-membered heterocyclic rings (S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: tetrathiopyrans; tetrathiazines; tetrathiaphosphorins; tetrathiadiphosphorins; tetraoxathiins; and tetradithiins.
[0429] S Valence Stabilizer #16b: Examples of five-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all five binding sites are composed of sulfur and are contained in component 6-membered heterocyclic rings (S—S Tridentates or S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: pentathiopyrans; pentathiazines; pentathiaphosphorins; pentathiadiphosphorins; pentaoxathiins; and pentadithins.
[0430] S Valence Stabilizer #16c: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of sulfur and are contained in component 6-membered heterocyclic rings (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: hexathiopyrans; hexathiazines; hexathiaphosphorins; hexathiadiphosphorins; hexaoxathiins; and hexadithiins.
[0431] S Valence Stabilizer #16d: Examples of seven-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all seven binding sites are composed of sulfur and are contained in component 6-membered heterocyclic rings (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: heptathiopyrans; heptathiazines; heptathiaphosphorins; heptathiadiphosphorins; heptaoxathiins; and heptadithiins.
[0432] S Valence Stabilizer #16e: Examples of eight-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all eight binding sites are composed of sulfur and are contained in component 6-membered heterocyclic rings (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: octathiopyrans; octathiazines; octathiaphosphorins; octathiadiphosphorins; octaoxathiins; and octadithiins.
[0433] S Valence Stabilizer #16f: Examples of nine-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all nine binding sites are composed of sulfur and are contained in component 6-membered heterocyclic rings (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+ include, but are not limited to: nonathiopyrans; nonathiazines; nonathiaphosphorins; nonathiadiphosphorins; nonaoxathiins; and nonadithiins.
[0434] S Valence Stabilizer #16g: Examples of ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all ten binding sites are composed of sulfur and are contained in component 6-membered heterocyclic rings (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: decathiopyrans; decathiazines; decatbiaphosphorins; decathiadiphosphorins; decaoxathiins; and decadithiins.
[0435] S Valence Stabilizer #17a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of sulfur and are contained in a combination of 6-membered heterocyclic rings and thiol, thioether, or thioketo groups (S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiatetrathiopyrans; tetrathiatetrathiopyrans; dithiatetrathiazines; tetrathiatetrathiazines; dithiatetrathiaphosphorins; tetrathiatetrathiaphosphorins; dithiatetraoxathiins; tetrathiatetraoxathiins; dithiatetradithiins; and tetrathiatetradithiins.
[0436] S Valence Stabilizer #17b: Examples of five-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all five binding sites are composed of sulfur and are contained in a combination of 6-membered heterocyclic rings and thiol, thioether, or thioketo groups (S—S Tridentates or S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiapentathiopyrans; tetrathiapentathiopyrans; dithiapentathiazines; tetrathiapentathiazines; dithiapentathiaphosphorins; tetrathiapentathiaphosphorins; dithiapentaoxathiins; tetrathiapentaoxathiins; dithiapentadithiins; and tetrathiapentadithiins.
[0437] S Valence Stabilizer #17c: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of sulfur and are contained in a combination of 6-membered heterocyclic rings and thiol, thioether, or thioketo groups (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiahexathiopyrans; trithiahexathiopyrans; dithiahexathiazines; trithiahexathiazines; dithiahexathiaphosphorins; trithiahexathiaphosphorins; dithiahexaoxathiins; trithiahexaoxathiins; dithiahexadithiins; and trithiahexadithiins.
[0438] S Valence Stabilizer #17d: Examples of seven-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all seven binding sites are composed of sulfur and are contained in a combination of 6-membered heterocyclic rings and thiol, thioether, or thioketo groups (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiaheptathiopyrans; tetrathiaheptathiopyrans; dithiaheptathiazines; tetrathiaheptathiazines; dithiaheptathiaphosphorins; tetrathiaheptathiaphosphorins; dithiaheptaoxathiins; tetrathiaheptaoxathiins; dithiaheptadithiins; and tetrathiaheptadithiins.
[0439] S Valence Stabilizer #17e: Examples of eight-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all eight binding sites are composed of sulfur and are contained in a combination of 6-membered heterocyclic rings and thiol, thioether, or thioketo groups (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiaoctathiopyrans; tetrathiaoctathiopyrans; dithiaoctathiazines; tetrathiaoctathiazines; dithiaoctathiaphosphorins; tetrathiaoctathiaphosphorins; dithiaoctaoxathiins; tetrathiaoctaoxathiins; dithiaoctadithiins; and tetrathiaoctadithiins.
[0440] S Valence Stabilizer #17f: Examples of nine-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all nine binding sites are composed of sulfur and are contained in a combination of 6-membered heterocyclic rings and thiol, thioether, or thioketo groups (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: trithianonathiopyrans; hexathianonathiopyrans; trithianonathiazines; hexathianonathiazines; trithianonathiaphosphorins; hexathianonathiaphosphorins; trithianonaoxathiins; hexathianonaoxathiins; trithianonadithiins; and hexathianonadithiins.
[0441] S Valence Stabilizer #17g: Examples of ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all ten binding sites are composed of sulfur and are contained in a combination of 6-membered heterocyclic rings and thiol, thioether, or thioketo groups (S—S Tridentates, S—S Tetradentates, or S—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiadecathiopyrans; pentathiadecathiopyrans; dithiadecathiazines; pentathiadecathiazines; dithiadecathiaphosphorins; pentathiadecathiaphosphorins; dithiadecaoxathiins; pentathiadecaoxathiins; dithiadecadithins; and pentathiadecadithiins.
[0442] S Valence Stabilizer #18: Examples of dithiobiurets (dithioimidodicarbonic diamides), dithioisobiurets, dithiobiureas, trithiotriurets, trithiotriureas, bis(dithiobiurets), bis(dithioisobiurets), bis(dithiobiureas), poly(dithiobiurets), poly(dithioisobiurets), and poly(dithiobiureas) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiobiuret, dithioisobiuret, dithiobiurea, trithiotriuret, trithiotriurea, nitrodithiobiuret, dinitrodithiobiuret, aminodithiobiuret, diaminodithiobiuret, oxydithiobiuret, dioxydithiobiuret, cyanodithiobiuret, methyldithiobiuret, ethyldithiobiuret, isopropyldithiobiuret, phenyldithiobiuret, benzyldithiobiuret, cyclohexyldithiobiuret, norbornyldithiobiuret, adamantyldithiobiuret, dimethyldithiobiuret, diethyldithiobiuret, diisopropyldithiobiuret, diphenyldithiobiuret, dibenzyldithiobiuret, dicyclohexyldithiobiuret, dinorbornyldithiobiuret, and diadamantyldithiobiuret.
[0443] S Valence Stabilizer #19: Examples of thioacylthioureas, thioaroylthioureas, bis(thioacylthioureas), bis(thioaroylthioureas), poly(thioacylthioureas), and poly(thioaroylthioureas) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: thioformylthiourea, thioacetylthiourea, thiobenzoylthiourea, thiocyclohexoylthiourea, pentafluorothiobenzoylthiourea, N-methylthioacetylthiourea, N-phenylthiobenzoylthiourea, and N-cyclohexylthiocyclohexoylthiourea.
[0444] S Valence Stabilizer #20: Examples of dithioacyl disulfides, bis(dithioacyl disulfides), and poly(dithioacyl disulfides), (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithioacetyl disulfide; dithiopropanoyl disulfide; dithiobenzoyl disulfide; and dithiopentafluorobenzoyl disulfide.
[0445] S Valence Stabilizer #21: Examples of tetrathioperoxydicarbonic diamides, bis(tetrathioperoxydicarbonic diamides), and poly(tetrathioperoxydicarbonic diamides) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: tetrathioperoxydicarbonic diamide; N-phenyltetrathioperoxydicarbonic diamide; N-benzyltetrathioperoxydicarbonic diamide; N-cyclohexyltetrathioperoxydicarbonic diamide; N-norbornyltetrathioperoxydicarbonic diamide; N,N′-diphenyltetrathioperoxydicarbonic diamide; N,N′-dibenzyltetrathioperoxydicarbonic diamide; N,N′-dicyclohexyltetrathioperoxydicarbonic diamide; and N,N′-dinorbornyltetrathioperoxydicarbonic diamide.
[0446] S Valence Stabilizer #22: Examples of hexathio-, pentathio-, and tetrathioperoxydicarbonic acids, bis(hexathio-, pentathio-, and tetrathioperoxydicarbonic acids), poly(hexathio-, pentathio-, and tetrathioperoxydicarbonic acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: hexathioperoxydicarbonic acid, pentathioperoxydicarbonic acid, tetrathioperoxydicarbonic acid, S-phenylhexathioperoxydicarbonic acid; S-benzylhexathioperoxydicarbonic acid; S-cyclohexylhexathioperoxydicarbonic acid; S-norbornylhexathioperoxydicarbonic acid; S,S′-diphenylhexathioperoxydicarbonic acid; S,S′dibenzylhexathioperoxydicarbonic acid; S,S′-dicyclohexylhexathioperoxydicarbonic acid; and S,S′-dinorbornylhexathioperoxydicarbonic acid.
[0447] S Valence Stabilizer #23: Examples of dithioperoxydiphosphoramides, bis(dithioperoxydiphosphoramides), and poly(dithioperoxydiphosphoramides) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithioperoxydiphosphoramide, N-methyldithioperoxydiphosphoramide, N-isopropyldithioperoxydiphosphoramide, N-tert-butyldithioperoxydiphosphoramide, N-phenyldithioperoxydiphosphoramide, N-pentafluorophenyldithioperoxydiphosphoramide, N-benzyldithioperoxydiphosphoramide, N-cyclohexyldithioperoxydiphosphoramide, N-norbornyldithioperoxydiphosphoramide, N,N′″-dimethyldithioperoxydiphosphoramide, N,N′″-diisopropyldithioperoxydiphosphoramide, N,N′″-di-tert-butyldithioperoxydiphosphoramide, N,N′″-diphenyldithioperoxydiphosphoramide, N,N′″-di-pentafluorophenyldithioperoxydiphosphoramide, N,N′″-dibenzyldithioperoxydiphosphoramide, N,N′″-dicyclohexyldithioperoxydiphosphoramide, and N,N′″-dinorbornyldithioperoxydiphosphoramide.
[0448] S Valence Stabilizer #24: Examples of dithioperoxydiphosphoric acids, bis(dithioperoxydiphosphoric acids), poly(dithioperoxydiphosphoric acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithioperoxydiphosphoric acid, methyldithioperoxydiphospboric acid, isopropyldithioperoxydiphosphoric acid, tert-butyldithioperoxydiphosphoric acid, phenyldithioperoxydiphosphoric acid, pentafluorophenyldithioperoxydiphosphoric acid, benzyldithioperoxydiphosphoric acid, cyclohexyldithioperoxydiphosphoric acid, norbornyldithioperoxydiphosphoric acid, dimethyldithioperoxydiphosphoric acid, diisopropyldithioperoxydiphosphoric acid, di-tert-butyldithioperoxydiphosphoric acid, diphenyldithioperoxydiphosphoric acid, di-pentafluoropbenyldithioperoxydiphosphori c acid, dibenzyldithioperoxydiphosphoric acid, dicyclohexyldithioperoxydiphosphoric acid, and dinorbornyldithioperoxydiphosphoric acid.
[0449] S Valence Stabilizer #25: Examples of dithioimidodiphosphonic acids, dithiohydrazidodiphosphonic acids, bis(dithioimidodiphosphonic acids), bis(dithiohydrazidodipbosphonic acids), poly(dithioimidodiphosphonic acids), poly(dithiohydrazidodiphosphonic acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithioimidodiphosphonic acid, methyldithioimidodiphosphonic acid, isopropyldithioimidodiphosphonic acid, tert-butyldithioimidodiphospbonic acid, phenyldithioimidodiphosphonic acid, pentafluorophenyldithioimidodiphosphonic acid, benzyldithioimidodiphosphonic acid, cyclohexyldithioimidodiphosphonic acid, norbornyldithioimidodiphosphonic acid, dimethyldithioimidodiphosphonic acid, diisopropyldiothioimidodiphosphonic acid, di-tert-butyldithioimidodiphosphonic acid, diphenyldithioimidodipbosphonic acid, di-pentafluorophenyldithioimidodiphosphonic acid, dibenzyldithioimidodiphosphonic acid, dicyclohexyldithioimidodiphosphonic acid, and dinorbornyldithioimidodiphosphonic acid. [Note: The phosphite (P+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]
[0450] S Valence Stabilizer #26: Examples of dithioimidodiphosphonamides, dithiohydrazidodiphosphonamides, bis(dithioimidodiphosphonamides), bis(dithiohydrazidodiphosphonamides), poly(dithioimidodiphosphonamides), and poly(dithiohydrazidodiphosphonamides) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithioimidodiphosphonamide, N-methyldithioimidodiphosphonamide, N-isopropyl dithioimidodiphosphonamide, N-tert-butyldithioimidodiphosphonamide, N-phenyldithioimidodiphosphonamide, N-pentafluorophenyldithioimidodiphosphonamide, N-benzyldithioimidodiphosphonamide, N-cyclohexyldithioimidodiphosphonamide, N-norbornyldithioimidodiphosphonamide, N,N′″-dimethyldithioimidodiphosphonamide, N,N′″-diisopropyldithioimidodiphosphonamide, N,N′″-di-tert-butyldithioimidodiphosphonamide, N,N′″-diphenyldithioimidodiphosphonamide, N,N′″-di-pentafluorophenyldithioimidodiphosphonamide, N,N′″-dibenzyldithioimidodiphosphonamide, N,N′″-dicyclohexyldithioimidodiphosphonamide, and N,N′″-dinorbornyldithioimidodiphosphonamide. [Note: The phosphite (p+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]
[0451] S Valence Stabilizer #27: Examples of dithiodiphosphonamides, bis(dithiodiphosphonamides), and poly(dithiodiphosphonamides) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meetthe requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiodiphosphonamide, N-methyldithiodiphosphonamide, N-isopropyldithiodiphosphonamide, N-tert-butyldithiodiphosphonamide, N-phenyldithiodiphosphonamide, N-pentafluorophenyldithiodiphosphonamide, N-benzyldithiodiphosphonamide, N-cyclohexyldithiodiphosphonamide, N-norbornyldithiodiphosphonamide, N,N′″-dimethyldithiodiphosphonamide, N,N′″-diisopropyldithiodiphosphonamide, N,N′″-di-tert-butyldithiodiphosphonamidc, N,N′″-diphenyldithiodiphosphonamide, N,N′″-di-pentafluorophenyldithiodiphosphonamide, N,N′″-dibenzyldithiodiphosphonamide, N,N′″-dicyclohexyldithiodiphosphonamide, and N,N′″-dinorbornyldithiodiphosphonamide. [Note: The phosphite (P+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]
[0452] S Valence Stabilizer #28: Examples of dithiodiphosphonic acids, bis(dithiodiphosphonic acids), poly(dithiodiphosphonic acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiodiphosphonic acid, methyldithiodiphosphonic acid, isopropyldithiodiphosphonic acid, tert-butyldithiodiphosphonic acid, phenyldithiodiphosphonic acid, pentafluorophenyldithiodiphosphonic acid, benzyldithiodiphosphonic acid, cyclohexyldithiodiphosphonic acid, norbornyldithiodiphosphonic acid, dimethyldithiodiphosphonic acid, diisopropyldiothiodiphosphonic acid, di-tert-butyldithiodiphosphonic acid, diphenyldithiodiphosphonic acid, di-pentafluorophenyldithiodiphosphonic acid, dib,enzyldithiodiphosphonic acid, dicyclohexyldithiodiphosphonic acid, and dinorbornyldithiodiphosphonic acid. [Note: The phosphite (P+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]
[0453] S Valence Stabilizer #29: Examples of dithioperoxydiphosphonamides, bis(dithioperoxydiphosphonamides), and poly(dithioperoxydiphosphonamides) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithioperoxydiphosphonamide, N-methyldithioperoxydiphosphonamide, N-isopropyldithioperoxydiphosphonamide, N-tert-butyldithioperoxydiphosphonamide, N-phenyldithioperoxydiphosphonamide, N-pentafluorophenyldithioperoxydiphosphonamide, N-benzyldithioperoxydiphosphonamide, N-cyclohexyldithioperoxydiphosphonamide, N-norbornyldithioperoxydiphosphonamide, N,N′″-dimethyldithioperoxydiphosphonamide, N,N′″-diisopropyldithioperoxydiphosphonamide, N,N′″-di-tert-butyldithioperoxydiphosphonamide, N,N′″-diphenyldithioperoxydiphosphonamide, N,N′″-di-pentafluorophenyldithioperoxydiphosphonamide, N,N′″-dibenzyldithioperoxydiphosphonamide, N,N′″-dicyclohexyldithioperoxydiphosphonamide, and N,N′″-dinorbornyldithioperoxydiphosphonamide. [Note: The phosphite (P+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]
[0454] S Valence Stabilizer #30: Examples of dithioperoxydiphosphonic acids, bis(dithioperoxydiphosphonic acids), poly(dithioperoxydiphosphonic acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithioperoxydiphosphonic acid, methyldithioperoxydiphosphonic acid, isopropyldithioperoxydiphosphonic acid, tert-butyldithioperoxydiphosphonic acid, phenyldithioperoxydiphosphonic acid, pentafluorophenyldithioperoxydiphosphonic acid, benzyldithioperoxydiphosphonic acid, cyclohexyldithioperoxydiphosphonic acid, norbornyldithioperoxydiphosphonic acid, dimethyldithioperoxydiphosphonic acid, diisopropyldithioperoxydiphosphonic acid, di-tert-butyldithioperoxydiphosphonic acid, diphenyldithioperoxydiphosphonic acid, di-pentafluorophenyldithioperoxydiphosphonic acid, dibenzyldithioperoxydiphosphonic acid, dicyclohexyldithioperoxydiphosphonic acid, and dinorbornyldithioperoxydiphosphonic acid. [Note: The phosphite (P+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]
[0455] S Valence Stabilizer #31: Examples of dithiophosphonic acids (phosphonodithioic acids), bis(dithiophosphonic acids), poly(dithiophosphonic acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiophosphonic acid, O-phenyldithiophosphonic acid, O-benzyldithiophosphonic acid, O-cyclohexyldithiophosphonic acid, O-norbornyldithiophosphonic acid, O,P-diphenyldithiophosphonic acid, O,P-dibenzyldithiophosphonic acid, O,P-dicyclohexyldithiophosphonic acid, and O,P-dinorbornyldithiophosphonic acid. [Note: The phosphite (P+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]
[0456] S Valence Stabilizer #32: Examples of trithiophosphonic acids (phosphonotrithioic acids), bis(trithiophosphonic acids), poly(trithiophosphonic acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: trithiophosphonic acid, S-phenyltrithiophosphonic acid, S-benzyltrithiophosphonic acid, S-cyclohexyltrithiophosphonic acid, S-norbornyltrithiophosphonic acid, S,P-diphenyltrithiophosphonic acid, S,P-dibenzyltrithiophosphonic acid, S,P-dicyclohexyltrithiophosphonic acid, and S,P-dinorbornyltrithiophosphonic acid. [Note: The phosphite (P+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.] S Valence Stabilizer #33: Examples of phosphono(dithioperoxo)thioic acids, bis[phosphono(dithioperoxo)thioic acids], poly[phosphono(dithioperoxo)thioic acids], and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: phosphono(dithioperoxo)thioic acid, O-phenylphosphono(dithioperoxo)thioic acid, O-benzylphosphono(dithioperoxo)thioic acid, O-cyclohexylphosphono(dithioperoxo)thioic acid, O-norbornylphosphono(dithioperoxo)thioic acid, O,P-diphenylphosphono(dithioperoxo)thioic acid, O,P-dibenzylphosphono(dithioperoxo)thioic acid, O,P-dicyclohexylphosphono(dithioperoxo)thioic acid, and O,P-dinorbornylphosphono(dithioperoxo)thioic acid. [Note: The phosphite (P+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]
[0457] S Valence Stabilizer #34: Examples of phosphono(dithioperoxo)dithioic acids, bis[phosphono(dithioperoxo)dithioic acids], poly[phosphono(dithioperoxo)dithioic acids], and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: phosphono(dithioperoxo)dithioic acid, S-phenylphosphono(dithioperoxo)dithioic acid, S-benzylphosphono(dithioperoxo)dithioic acid, S-cyclohexylphosphono(dithioperoxo)dithioic acid, S-norbornylphosphono(dithioperoxo)dithioic acid, S,P-diphenylphosphono(dithioperoxo)dithioic acid, S,P-dibenzylphosphono(dithioperoxo)dithioic acid, S,P-dicyclohexylphosphono(dithioperoxo)dithioic acid, and S,P-dinorbornylphosphono(dithioperoxo)dithioic acid. [Note: The phosphite (P+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]
[0458] S Valence Stabilizer #35: Examples of S-(alkylthio)thiocarboxylic acids, S-(arylthio)thiocarboxylic acids, and S,S-thiobisthiocarboxylic Acids (S—S Bidentates and S—S Tridentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: (methylthio)thioacetic acid; (methylthio)thiobenzoic acid; (methylthio)thionicotinic acid; (methylthio)thionapthoic acid; (phenylthio)thioacetic acid; (phenylthio)thiobenzoic acid; (phenylthio)thionaphthoic acid; (norbornylthio)thioacetic acid; (norbornylthio)thiobenzoic acid; (norbornylthio)thionapthoic acid; thiobisthioacetic acid; thiobisthiobenzoic acid; and thiobisthionapthoic acid.
[0459] S Valence Stabilizer #36: Examples of S-(alkyldisulfido)thiocarboxylic acids, S-(aryldisulfido)thiocarboxylic acids, and S,S′-disulfidobisthiocarboxylic acids (S—S Bidentates and S—S Tridentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: (methyldisulfido)thioacetic acid; (methyldisulfido)thiobenzoic acid; (methyldisulfido)thionicotinic acid; (methyldisulfido)thionapthoic acid; (phenyldisulfido)thioacetic acid; (phenyldisulfido)thiobenzoic acid; (phenyldisulfido)thionaphthoic acid; (norbornyldisulfido)thioacetic acid; (norbornyldisulfido)thiobenzoic acid; (norbornyldisulfido)thionapthoic acid; S,S′-disulfidobisthioacetic pacid; S,S′-disulfidobisthiobenzoic acid; and S,S′-disulfidobisthionapthoic acid.
[0460] S Valence Stabilizer #37: Examples of 1,2-dithiolates, bis(1,2-dithiolates), and poly(1,2-dithiolates) (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2,3-butanedithiol; 1,2-diphenyl-1,2-ethanedithiol; 1,2-di(pentafluorophenyl)-1,2-ethanedithio; 1,2-dicyclohexyl-1,2-ethanedithiol; 1,2-dinorbornyl-1,2-ethanedithiol; 2,3-dimercaptopropanol; 2,3-dimercaptosuccinic acid; poly[bis(arylthio)acetylene]s; and poly[bis(alkylylthio)acetylene]s.
[0461] S Valence Stabilizer #38: Examples of rhodanines and bis(rhodanines) (S—S Bidentates and S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 3-methylrhodanine; 3-ethylrhodanine; 3-isopropylrhodanine; 3-phenylrhodanine; 3-benzylrhodanine; 3-cyclohexylrhodanine; 3-norbornylrhodanine; 5-methylrhodanine; 5-ethylrhodanine; 5-isopropylrhodanine; 5-phenylrhodanine; 5-benzylrhodanine; 5-cyclohexylrhodanine; 5-norbornylrhodanine; 3,3′-ethylenebisrhodanine; 3,3′-propylenerhodanine; 3,3′-butylenerhodanine; 5,5′-ethylenebisrhodanine; 5,5′-propylenerhodanine; and 5,5′-butylenerhodanine. [Note: rhodanines and bis(rhodanines) tend to stabilize lower oxidation states in metal ions.]
[0462] S Valence Stabilizer #39: Examples of dithiocarbimates, bis(dithiocarbimates), and poly(dithiocarbimates) (S—S Bidentates, S—S Tridentates, and S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: methyldithiocarbimate; trifluoromethyldithiocarbimate; ethyldithiocarbimate; propyldithiocarbimate; isopropyldithiocarbimate; butyldithiocarbimate; tertbutyldithiocarbimate; cyanodithiocarbimate (CDC); cyanamidodithiocarbimate; azidodithiocarbimate; phenyldithiocarbimate; pentafluorophenyldithiocarbimate; benzyldithiocarbimate; naphthyldithiocarbimate; cyclohexyldithiocarbimate; norbornyldithiocarbimate; and adamantyldithiocarbimate. [Note: Carbimates tend to stabilize lower oxidation states in metal ions.]
[0463] S Valence Stabilizer #40: Examples of thioxanthates, bis(thioxanthates), and poly(thioxanthates) (S—S Bidentates and S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: methyl thioxanthate (MeSxan); ethyl thioxanthate (EtSxan); isopropyl thioxanthate (iPrSxan); trifluoromethyl thioxanthate (CF3Sxan); cyanothioxanthate; cyanamidothioxanthate; phenyl thioxanthate (PhSxan); benzyl thioxanthate (BzSxan); pentafluorophenyl thioxanthate; cyclohexyl thioxanthate (cHxSxan); and norbornyl thioxanthate. [Note: Thioxanthates tend to stabilize lower oxidation states in metal ions.]
[0464] S Valence Stabilizer #41: Examples of xanthates, bis(xanthates), and poly(xanthates) (S—S Bidentates and S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: methyl xanthate (Mexan); ethyl xanthate (Etxan); isopropyl xanthate (iPrxan); trifluoromethyl xanthate (CF3xan); cyanoxanthate; cyanamidoxanthate; phenyl xanthate (Phxan); benzyl xanthate (Bzxan); pentafluorophenyl xanthate; cyclohexyl xanthate (cHxxan); and norbornyl xanthate. [Note: Xanthates tend to stabilize lower oxidation states in metal ions.]
[0465] S Valence Stabilizer #42: Examples of phosphinodithioformates (S—S Bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: trimethylphosphinodithioformate; triethylphosphinodithioformate; triphenylphosphinodithioformate; tricyclohexylphosphinodithioformate; dimethylphosphinodithioformate; diethylphosphinodithioformate; diphenylphosphinodithioformate; and dicyclohexylphosphinodithioformate.
[0466] S Valence Stabilizer #43: Examples of alkyl- and aryl-dithioborates, trithioborates, perthioborates, bis(dithioborates), bis(trithioborates), and bis(perthioborates) (S—S Bidentates and S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: S,O-diethyl dithioborate; S,O-diisopropyl dithioborate; S,O-diphenyl dithioborate; S,O-dibenzyl dithioborate; S,O-dicyclohexyl dithioborate; S,O-dinorbornyl dithioborate; diethyl trithioborate; diisopropyl trithioborate; diphenyl trithioborate; dibenzyl trithioborate; dicyclohexyl trithioborate; and dinorbornyl trithioborate.
[0467] S Valence Stabilizer #44: Examples of alkyl- and aryl-dithioboronates and bis(dithioboronates) (S—S Bidentates and S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diethyl dithioboronate; diisopropyl dithioboronate; diphenyl dithioboronate; dibenzyl dithioboronate; dicyclohexyl dithioboronate; and dinorbornyl dithioboronate. [Note: boronates tend to stabilize lower oxidation states in metal ions.]
[0468] S Valence Stabilizer #45: Examples of trithioarsonic acids (arsonotrithioic acids), dithioarsonic acids (arsonodithioic acids), tetrathioarsonic acids (arsonotetrathioic acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: trithioarsonic acid, O-phenyltrithioarsonic acid, O-benzyltrithioarsonic acid, O-cyclohexyltrithioarsonic acid, O-norbornyltrithioarsonic acid, O,S-diphenyltrithioarsonic acid, O,S-dibenzyltrithioarsonic acid, O,S-dicyclohexyltrithioarsonic acid, O,S-dinorbornyltrithioarsonic acid; dithioarsonic acid, O-phenyldithioarsonic acid, O-benzyldithioarsonic acid, O-cyclohexyldithioarsonic acid, O-norbornyldithioarsonic acid, O,O-diphenyldithioarsonic acid, O,O-dibenzyldithioarsonic acid, O,O-dicyclohexyldithioarsonic acid, and O,O-dinorbornyldithioarsonic acid.
[0469] S Valence Stabilizer #46: Examples of trithioantimonic acids (stibonotrithioic acids), dithioantimonic acids (stibonodithioic acids), tetrathioantimonic acids (stibonotetrathioic acids), and derivatives thereof (S—S Bidentates, S—S Tridentates, S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+ include, but are not limited to: trimethyltrithioantimonate; triethyltrithioantimonate; and triphenyltrithioantimonate.
[0470] S Valence Stabilizer #47: Examples of phosphine P-sulfides and amino-substituted phosphine sulfides (S Monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: trimethylphosphine sulfide (TMPS); triethylphosphine sulfide (TEPS); triphenylphosphine sulfide (TPhPS); tribenzylphosphine sulfide (TBzPS); tricyclohexylphosphine sulfide (TcHxPS); and trinorbornylphosphine sulfide for phosphine P-sulfides; and tris(dimethylamino)phosphine sulfide; trimorpholinophosphine sulfide; tripiperidinophosphine sulfide; tripyrrolidinophosphine sulfide; and tri(cyclohexylamino)phosphine sulfide for amino-substituted phosphine sulfides.
[0471] S Valence Stabilizer #48: Examples of arsine As-sulfides and amino-substituted arsine sulfides (S Monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: trimethylarsine sulfide; triethylarsine sulfide; triphenylarsine sulfide; tribenzylarsine sulfide; tricyclohexylarsine sulfide; and trinorbornylarsine sulfide for arsine As-sulfides; and tris(dimethylamino)arsine sulfide; trimorpholinoarsine sulfide; tripiperidinoarsine sulfide; tripyrrolidinoarsine sulfide; and tri(cyclohexylamino)arsine sulfide for amino-substituted arsine sulfides.
[0472] S Valence Stabilizer #49: Examples of thiolates that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: thiophenol; naphthalenethiol; 1-dodecanethion; hexadecyl mercaptan; benzenethiol (bt); polybenzenethiols; and polythioarylenes.
[0473] S Valence Stabilizer #50: Examples of sulfide that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: sulfides (—S2−); disulfides (—S22−); and polysulfides (—Sx2−).
[0474] P Valence Stabilizer #1: Examples of monophosphines (P monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: phosphine, phenylphosphine, diphenylphosphine, triphenylphosphine, tricyclohexylphosphine, phenyldimethylphosphine, phenyldiethylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, phosphirane, phosphetane, phospholane, phosphorinane, benzophospholane, benzophosphorinane, dibenzophospholane, dibenzophosphorinane, naphthophospholane, naphthophosphorinane, phosphinonorbornane, and phosphinoadamantane.
[0475] P Valence Stabilizer #2: Examples of diphosphines (P monodentates or P—P bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diphospholane, benzodiphospholane, naphthodiphospholane, diphosphorinane, benzodiphosphorinane, dibenzodiphosphorinane, naphthodiphosphorinane, bis(diphenylphosphino)methane, bis(diphenylphosphino)ethane, bis(diphenylphosphino)propane, bis(diphenylphosphino)butane, bis(diphenylphosphino)pentane, 1,2-bis(dipbenylphosphino)ethylene, and o-phenylenebis(diphenylphosphine). (Note: the aryl derivatives are air-stable, whereas the alkyl derivatives are air-sensitive and therefore unsuitable for these applications.)
[0476] P Valence Stabilizer #3: Examples of triphosphines (P monodentates, P—P bidentates, or P—P tridentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: triphosphorinane, P,P′-tetraphenyl-2-methyl-2-(P-diphenyl)phosphinomethyl-1,3-propanediphosphine; P,P-[2-(P-diphenyl)phosphinoethyl]diethyl-P-phenylphosphine; P,P-[2-(P-diphenyl)phosphino]diphenyl-P-phenylphosphine; and hexahydro-2,4,6-trimethyl-1,3,5-triphosphazine. (Note: the aryl derivatives are air-stable, whereas the alkyl derivatives are air-sensitive and therefore unsuitable for these applications.)
[0477] P Valence Stabilizer #4: Examples of tetraphosphines (P monodentates, P—P bidentates, P—P tridentates, and P—P tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: P,P′-tetraphenyl-2,2-[(P-diphenyl)phosphinomethyl]-1,3-propanediphosphine; tri[o-(P-diphenyl)phosphinophenyl]phosphine; and 1,1,4,7,10,10-hexaphenyl-1,4,7,10-tetraphosphadecane. (Note: the aryl derivatives are air-stable, whereas the alkyl derivatives are air-sensitive and therefore unsuitable for these applications.)
[0478] P Valence Stabilizer #5: Examples of pentaphosphines (P monodentates, P—P bidentates, P—P tridentates, and P—P tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 4-[2-(P-diphenyl)phosphinoethyl]-1,1,7,10,10-pentaphenyl-1,4,7,10-tetraphosphadecane. (Note: the aryl derivatives are air-stable, whereas the alkyl derivatives are air-sensitive and therefore unsuitable for these applications.)
[0479] P Valence Stabilizer #6: Examples of hexaphosphines (P—P bidentates, P—P tridentates, P—P tetradentates, and P—P hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 1,1,10,10-tetraphenyl-4,7-[2-(P,P-diphenyl)phosphinoethyl]-1,4,7,10-tetraphosphadecane. (Note: the aryl derivatives are air-stable, whereas the alkyl derivatives are air-sensitive and therefore unsuitable for these applications.)
[0480] P Valence Stabilizer #7a: Examples of 5-membered heterocyclic rings containing one phosphorus atom (P monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 1-phospholene, 2-phospholene, 3-phospholene, phosphole, oxaphosphole, thiaphosphole, benzophospholene, benzophosphole, benzoxaphosphole, benzothiaphosphole, dibenzophospholene, dibenzophosphole, naphthophospholene, naphthophosphole, naphthoxaphosphole, naphthothiaphosphole.
[0481] P Valence Stabilizer #7b: Examples of 5-membered heterocyclic rings containing two phosphorus atoms (P monodentates or P—P bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diphospholene, diphosphole, oxadiphospholene, thiadiphospholene, benzodiphospholene, benzodiphosphole, naphthodiphospholene, and naphthodiphosphole.
[0482] P Valence Stabilizer #7c: Examples of 5-membered heterocyclic rings containing three phosphorus atoms (P monodentates or P—P bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: triphosphole.
[0483] P Valence Stabilizer #8a: Examples of 6-membered heterocyclic rings containing one phosphorus atom (P monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: phosphorin, oxaphosphorin, thiaphosphorin, benzophosphorin, benzoxaphosphorin, benzothiaphosphorin, acridophosphine, phosphanthridine, dibenzoxaphosphorin, dibenzothiaphosphorin, naphthophosphorin, naphthoxaphosphorin, and naphthothiaphosphorin.
[0484] P Valence Stabilizer #8b: Examples of 6-membered heterocyclic rings containing two phosphorus atoms (P monodentates or P—P bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: o-diphosphorin, m-diphosphorin, p-diphosphorin, oxadiphosphorin, thiadiphosphorin, benzodiphosphorin, benzoxadiphosphorin, benzothiadiphosphorin, dibenzodiphosphorin, dibenzoxadiphosphorin, dibenzothiadiphosphorin, naphthodiphosphorin, naphthoxadiphosphorin, and naphthothiadiphosphorin.
[0485] P Valence Stabilizer #8c: Examples of 6-membered heterocyclic rings containing three phosphorus atoms (P monodentates or P—P bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 1,3,5-triphosphorin, 1,2,3-triphosphorin, benzo-1,2,3-triphosphorin, and naphtho-1,2,3-triphosphorin.
[0486] P Valence Stabilizer #9a: Examples of 5-membered heterocyclic rings containing one phosphorus atom and having at least one additional phosphorus atom binding site not contained in a ring (P Monodentates, P—P Bidentates, P—P Tridentates, P—P Tetradentates, or P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-(P-phenylphosphino)-1-phospholene; 2,5-(P-phenylphosphino)-phospholene; 2-(P-phenylphosphino)-3-phospholene; 2,5-(P-phenylphosphino)-3-phospholene; 2-(P-phenylphosphino)phosphole; 2,5-(P-phenylphosphino)phosphole; 2-(P-phenylphosphino)benzophosphole; 7-(P-phenylphosphino)benzophosphole; and 1,8-(P-phenylphosphino)dibenzophosphole.
[0487] P Valence Stabilizer #9b: Examples of 5-membered heterocyclic rings containing two phosphorus atoms and having at least one additional phosphorus atom binding site not contained in a ring (P Monodentates, P—P Bidentates, P—P Tridentates, P—P Tetradentates, or P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-(P-phenylphosphino)-1,3-diphospholene; 2,5-(P-phenylphosphino)-1,3-diphospholene; 2-(P-phenylphosphino)-1,3-diphosphole; 2,5-(P-phenylphosphino)-1,3-diphosphole; 2-(P-phenylphosphino)benzodiphosphole; and 7-(P-phenylphosphino)benzodiphosphole.
[0488] P Valence Stabilizer #9c: Examples of 5-membered heterocyclic rings containing three phosphorus atoms and having at least one additional phosphorus atom binding site not contained in a ring (P Monodentates, P—P Bidentates, P—P Tridentates, P—P Tetradentates, or P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-(P-phenylphosphino)-1,3,4-triphosphole; and 2,5-(P-phenylphosphino)-1,3,4-triphosphole.
[0489] P Valence Stabilizer #10a: Examples of 6-membered heterocyclic rings containing one phosphorus atom and having at least one additional phosphorus atom binding site not contained in a ring (P Monodentates, P—P Bidentates, P—P Tridentates, P—P Tetradentates, or P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-(P-phenylphosphino)phosphorin; 2,5-(P-phenylphosphino)phosphorin; 2-(P-phenylphosphino)benzophosphorin; 7-(P-phenylphosphino)benzophosphorin; and 1,9-(P-phenylphosphino)acridophosphine.
[0490] P Valence Stabilizer #10b: Examples of 6-membered heterocyclic rings containing two phosphorus atoms and having at least one additional phosphorus atom binding site not contained in a ring (P Monodentates, P—P Bidentates, P—P Tridentates, P—P Tetradentates, or P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-(P-phenylphosphino)-4-diphosphorin; 2,6-(P-phenylphosphino)-4-diphosphorin; 2,3,5,6-(P-phenylphosphino)-4-diphosphorin; 2-(P-phenylphosphino)benzo-1,4-diphosphorin; 2,3-(P-phenylphosphino)benzo-1,4-diphosphorin; 2,8-(P-phenylphosphino)benzo-1,4-diphosphorin; 2,3,5,8-(P-phenylphosphino)benzo-1,4-diphosphorin; 1,9-(P-phenylphosphino)dibenzodiphosphorin; and 1,4,6,9-(P-phenylphosphino)dibenzodiphosphorin.
[0491] P Valence Stabilizer #10c: Examples of 6-membered heterocyclic rings containing three phosphorus atoms and having at least one additional phosphorus atom binding site not contained in a ring (P Monodentates, P—P Bidentates, P—P Tridentates, P—P Tetradentates, or P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-(P-phenylphosphino)-1,3,5-triphosphorin; 2,6-(P-phenylphosphino)-1,3,5-triphosphorin; 4-(P-phenylphosphino)-1,2,3-triphosphorin; and 8-(P-phenylphosphino)benzo-1,2,3-triphosphorin.
[0492] P Valence Stabilizer #11a: Examples of 5-membered heterocyclic rings containing one phosphorus atom and having at least one additional phosphorus atom binding site contained in a ring (P Monodentates, P—P Bidentates, P—P Tridentates, P—P Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2,2′-bi-1-phospholene; 2,2′,2″-tri-1-phospholene; 2,2′-bi-3-phospholene; 2,2′, 2″-tri-3-phospholene; 2,2′-biphosphole; 2,2′,2″-triphosphole; and 2,2′-bibenzophosphole.
[0493] P Valence Stabilizer #11b: Examples of 5-membered heterocyclic rings containing two phosphorus atoms and having at least one additional phosphorus atom binding site contained in a ring (P Monodentates, P—P Bidentates, P—P Tridentates, P—P Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2,2′-bi-1,3-diphospholene; 2,2′-bi-1,3-diphosphole; and 2,2′-bibenzo-1,3-diphosphole.
[0494] P Valence Stabilizer #11c: Examples of 5-membered heterocyclic rings containing three phosphorus atoms and having at least one additional phosphorus atom binding site contained in a ring (P Monodentates, P—P Bidentates, P—P Tridentates, P—P Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2,2′-bi-1,3,4-triphosphole; and 2,2′,2″-tri-1,3,4-triphosphole.
[0495] P Valence Stabilizer #12a: Examples of 6-membered heterocyclic rings containing one phosphorus atom and having at least one additional phosphorus atom binding site contained in a ring (P Monodentates, P—P Bidentates, P—P Tridentates, P—P Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2,2′-biphosphorin; 2,2′,2″-triphosphorin; 2,2′,2″,2′″-tetraphosphorin; 2,2′-bibenzophosphorin; and 8,8′-bibenzophosphorin.
[0496] P Valence Stabilizer #12b: Examples of 6-membered heterocyclic rings containing two phosphorus atoms and having at least one additional phosphorus atom binding site contained in a ring (P Monodentates, P—P Bidentates, P—P Tridentates, P—P Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 3,3′-bi-1,2-diphosphorin; 3,3′,3″-tri-1,2-diphosphorin; 2,2′-bi-1,4-diphosphorin; 2,2′,2″-tri-1,4-diphosphorin; 3,3′-bibenzo-1,2-diphosphorin; 8,8′-bibenzo-1,2-diphosphorin; 2,2′-bibenzo-1,4-diphosphorin; and 8,8′-bibenzo-1,4-diphosphorin.
[0497] P Valence Stabilizer #12c: Examples of 6-membered heterocyclic rings containing three phosphorus atoms and having at least one additional phosphorus atom binding site contained in a ring (P Monodentates, P—P Bidentates, P—P Tridentates, P—P Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2,2′-bi-1,3,5-triphosphorin; 2,2′,2″-tri-1,3,5-triphosphorin; 4,4′-bi-1,2,3-triphosphorin; 4,4′-bibenzo-1,2,3-triphosphorin; and 8,8′-bibenzo-1,2,3-triphosphorin.
[0498] P Valence Stabilizer #13a: Examples of two-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein both binding sites are composed of phosphorus and are not contained in component heterocyclic rings (P—P Bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: P,P-diphenyldiphosphacyclobutane ([4]aneP2); P,P-diphenyldiphosphacyclopentane ([5]aneP2); P,P-diphenyldiphosphacyclohexane ([6]aneP2); P,P-diphenyldiphosphacycloheptane ([7]aneP2); P,P-diphenyldiphosphacyclooctane ([8]aneP2); P,P-diphenyldiphosphacyclobutene ([4]eneP2); P,P-diphenyldiphosphacyclopentene ([5]eneP2); P,P-diphenyldiphosphacyclohexene ([6]eneP2); P,P-diphenyldiphosphacycloheptene ([7]eneP2); and P,P-diphenyldiphosphacyclooctene ([8]eneP2).
[0499] P Valence Stabilizer #13b: Examples of three-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of phosphorus and are not contained in component heterocyclic rings (P—P Tridentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: P,P,P-triphenyltriphosphacyclohexane ([6]aneP3); P,P,P-triphenyltriphosphacycloheptane ([7]aneP3); P,P,P-triphenyltriphosphacyclooctane ([8]aneP3); P,P,P-triphenyltriphosphacyclononane ([9]aneP3); P,P,P-triphenyltriphosphacyclodecane ([10]aneP3); P,P,P-triphenyltriphosphacycloundecane ([11]aneP3); P,P,P-triphenyltriphosphacyclododecane ([12]aneP3); P,P,P-triphenyltriphosphacyclohexatriene ([6]trieneP3); P,P,P-triphenyltriphosphacycloheptatriene ([7]trieneP3); P,P,P-triphenyltriphosphacyclooctatriene ([8]trieneP3); P,P,P-triphenyltriphosphacyclononatriene ([9]trieneP3); P,P,P-triphenyltriphosphacyclodecatriene ([10]trieneP3); P,P,P-triphenyltriphosphacycloundecatriene ([11]trieneP3); and P,P,P-triphenyltriphosphacyclododecatriene ([12]trieneP3).
[0500] P Valence Stabilizer #13c: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of phosphorus and are not contained in component heterocyclic rings (P—P Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: P,P,P,P-tetraphenyltetraphosphacyclooctane ([8]aneP4); P,P,P,P-tetraphenyltetraphosphacyclononane ([9]aneP4); P,P,P,P-tetraphenyltetraphosphacyclodecane ([10]aneP4); P,P,P,P-tetraphenyltetraphosphacycloundecane ([11]aneP4); P,P,P,P-tetraphenyltetraphosphacyclododecane ([12]aneP4); P,P,P,P-tetraphenyltetraphosphacyclotridecane ([13]aneP4); P,P,P,P-tetraphenyltetraphosphacyclotetradecane ([14]aneP4); P,P,P,P-tetraphenyltetraphosphacyclopentadecane ([15]aneP4); P,P,P,P-tetraphenyltetraphosphacyclohexadecane ([16]aneP4); P,P,P,P-tetraphenyltetraphosphacycloheptadecane ([17]aneP4); P,P,P,P-tetraphenyltetraphosphacyclooctadecane ([18]aneP4); P,P,P,P-tetraphenyltetraphosphacyclononadecane ([19]aneP4); and P,P,P,P-tetraphenyltetraphosphacycloeicosane ([20]aneP4).
[0501] P Valence Stabilizer #13d: Examples of five-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of phosphorus and are not contained in component heterocyclic rings (P—P Tridentates, or P—P Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: P,P,P,P,P-pentaphenylpentaphosphacyclodecane ([10]aneP5); P,P,P,P,P-pentaphenylpentaphosphacycloundecane ([11]aneP5); P,P,P,P,P-pentaphenylpentaphosphacyclododecane ([12]aneP5); P,P,P,P,P-pentaphenylpentaphosphacyclotridecane ([13]aneP5); P,P,P,P,P-pentaphenylpentaphosphacyclotetradecane ([14]aneP5); and P,P,P,P,P-pentaphenylpentaphosphacyclopentadecane ([15]aneP5).
[0502] P Valence Stabilizer #13e: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of phosphorus and are not contained in component heterocyclic rings (P—P—P Tridentates, P—P—P—P Tetradentates, or P—P—P—P—P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: P,P,P,P,P,P-hexaphenylhexaphosphacyclododecane ([12]aneP6); P,P,P,P,P,P-hexaphenylhexaphosphacyclotridecane ([13]aneP6); P,P,P,P,P,P-hexaphenylhexaphosphacyclotetradecane ([14]aneP6); P,P,P,P,P,P-hexaphenylhexaphosphacyclopentadecane ([15]aneP6); P,P,P,P,P,P-hexaphenylhexaphosphacyclohexadecane ([16]aneP6); P,P,P,P,P,P-hexaphenylhexaphosphacycloheptadecane ([17]aneP6); P,P,P,P,P,P-hexaphenylhexaphosphacyclooctadecane ([18]aneP6); P,P,P,P,P,P-hexaphenylhexaphosphacyclononadecane ([19]aneP6); P,P,P,P,P,P-hexaphenylhexaphosphacycloeicosane ([20]aneP6); P,P,P,P,P,P-hexaphenylhexaphosphacycloheneicosane ([21]aneP6); P,P,P,P,P,P-hexaphenylhexaphosphacyclodocosane ([22]aneP6); P,P,P,P,P,P-hexaphenylhexaphosphacyclotricosane ([23]aneP6); P,P,P,P,P,P-hexaphenylhexaphosphacyclotetracosane ([24]aneP6).
[0503] P Valence Stabilizer #13f: Examples of eight-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of phosphorus and are not contained in component heterocyclic rings (P—P Tridentates, P—P Tetradentates, or P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: P,P,P,P,P,P,P,P-octaphenyloctaphosphacyclohexadecane ([16]aneP8); P,P,P,P,P,P,P,P-octaphenyloctaphosphacycloheptadecane ([17]aneP8); P,P,P,P,P,P,P,P-octaphenyloctaphosphacyclooctadecane ([18]aneP8); P,P,P,P,P,P,P,P-octaphenyloctaphosphacyclononadecane ([19]aneP8); P,P,P,P,P,P,P,P-octaphenyloctaphosphacycloeicosane ([20]aneP8); P,P,P,P,P,P,P,P-octaphenyloctaphosphacycloheneicosane ([21]aneP8); P,P,P,P,P,P,P,P-octaphenyloctaphosphacyclodocosane ([22]aneP8); P,P,P,P,P,P,P,P-octaphenyloctaphosphacyclotricosane ([23]aneP8); and P,P,P,P,P,P,P,P-octaphenyloctaphosphacyclotetracosane ([24]aneP8).
[0504] P Valence Stabilizer #14a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of phosphorus and are contained in component 5-membered heterocyclic rings (P—P Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: tetraphospholenes; tetraphospholes; tetraoxaphospholes; tetradiphospholenes; tetradiphospholes; and tetraoxadiphospholes.
[0505] P Valence Stabilizer #14b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of phosphorus and are contained in component 5-membered heterocyclic rings (P—P Tetradentates and P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: hexaphospholenes; hexaphospholes; hexaoxaphospholes; hexadiphospholenes; hexadiphospholes; and hexaoxadiphospholes.
[0506] P Valence Stabilizer #14c: Examples of eight-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all eight binding sites are composed of phosphorus and are contained in component 5-membered heterocyclic rings (P—P Tridentates; P—P Tetradentates; or P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: octaphospholenes; octaphospholes; octaoxaphospholes; octadiphospholenes; octadiphospholes; and octaoxadiphospholes.
[0507] P Valence Stabilizer #15a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of phosphorus and are contained in a combination of 5-membered heterocyclic rings and phosphine groups (P—P Tridentates, P—P Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diphosphatetraphospholenes; tetraphosphatetraphospholenes; dipbosphatetraphospholes; tetraphosphatetraphospholes; diphoshatetradiphospholes; and tetraphosphatetradiphospholes.
[0508] P Valence Stabilizer #15b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of phosphorus and are contained in a combination of 5-membered heterocyclic rings and phosphine groups (P—P Tridentates, P—P Tetradentates, and P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diphosphahexaphospholenes; triaphosphahexaphospholenes; diphosphahexaphospholes; triphosphahexaphospholes; diphoshahexadiphospholes; and triphosphahexadiphospholes.
[0509] P Valence Stabilizer #15c:—Examples of eight membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all eight binding sites are composed of phosphorus and are contained in a combination of 5-membered heterocyclic rings and phosphine groups (P—P Tridentates, P—P Tetradentates, and P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diphosphaoctaphospholenes; tetraphosphaoctaphospholenes; diphosphaoctaphospholes; tetraphosphaoctaphospholes; diphoshaoctadiphospholes; and tetraphosphaoctadiphospholes.
[0510] P Valence Stabilizer #16a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of phosphorus and are contained in component 6-membered heterocyclic rings (P—P Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: cyclotetraphosphorins; cyclotetraaoxaphosphorins; cyclotetradiphosphorins; and cyclotetraoxadiphosphorins.
[0511] P Valence Stabilizer #16b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of phosphorus and are contained in component 6-membered heterocyclic rings (P—P Tridentates, P—P Tetradentates, and P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+ include, but are not limited to: cyclohexaphosphorins; cyclohexaoxaphosphorins; cyclohexadiphosphorins; and cyclohexaoxadiphosphorins.
[0512] P Valence Stabilizer #16c: Examples of eight-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all eight binding sites are composed of phosphorus and are contained in component 6-membered heterocyclic rings (P—P Tridentates, P—P Tetradentates, and P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: cyclooctaphosphorins; cyclooctaoxaphosphorins; cyclooctadiphosphorins; and cyclooctaoxadiphosphorins.
[0513] P Valence Stabilizer #17a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of phosphorus and are contained in a combination of 6-membered heterocyclic rings and phosphine groups (P—P Tridentates, P—P Tetradentates, or P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diphosphacyclotetraphosphorins; tetraphosphacyclotetraphosphorins; diphosphacyclotetraoxaphosphorins; tetraphosphacyclotetraoxaphosphorins; diphosphacyclotetradiphosphorins; tetraphosphacyclotetradiphosphorins; diphosphacyclotetraoxadiphosphorins; and tetraphosphacyclotetraoxadiphosphorins.
[0514] P Valence Stabilizer #17b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of phosphorus and are contained in a combination of 6-membered heterocyclic rings and phosphine groups (P—P Tridentates, P—P Tetradentates, or P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diphosphacyclohexaphosphorins; triphosphacyclohexaphosphorins; diphosphacyclohexaoxaphosphorins; triphosphacyclohexaoxaphosphorins; diphosphacyclohexadiphosphorins; triphosphacyclohexadiphosphorins; diphosphacyclohexaoxadiphosphorins; and triphosphacyclohexaoxadiphosphorins.
[0515] P Valence Stabilizer #17c: Examples of eight-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all eight binding sites are composed of phosphorus and are contained in a combination of 6-membered heterocyclic rings and phosphine groups (P—P Tridentates, P—P Tetradentates, or P—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diphosphacyclooctaphosphorins; tetraphosphacyclooctaphosphorins; diphosphacyclooctaoxaphosphorins; tetraphosphacyclooctaoxaphosphorins; diphosphacyclooctadiphosphorins; -tetraphosphacyclooctadiphosphorins; diphosphacyclooctaoxadiphosphorins; and tetraphospbacyclooctaoxadiphosphorins.
[0516] O Valence Stabilizer #1: Examples of dithioperoxydicarbonic acids, bis(dithioperoxydicarbonic acids), poly(dithioperoxydicarbonic acids), and derivatives thereof (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithioperoxydicarbonic acid, O-phenyldithioperoxydicarbonic acid; O-benzyldithioperoxydicarbonic acid; O-cyclohexyldithioperoxydicarbonic acid; O-norbornyldithioperoxydicarbonic acid; O,O′-diphenyldithioperoxydicarbonic acid; O,O′-dibenzyldithioperoxydicarbonic acid; O,O′-dicyclohexyldithioperoxydicarbonic acid; and O,O′-dinorbornyldithioperoxydicarbonic acid.
[0517] O Valence Stabilizer #2: Examples of imidodiphosphonic acids, hydrazidodiphosphonic acids, bis(imidodiphosphonic acids), bis(hydrazidodiphosphonic acids), poly(imidodiphosphonic acids), poly(hydrazidodiphosphonic acids), and derivatives thereof (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: imidodiphosphonic acid, methylimidodiphosphonic acid, isopropylimidodiphosphonic acid, tert-butylimidodiphosphonic acid, phenylimidodiphosphonic acid, pentafluorophenylimidodiphosphonic acid, benzylimidodiphosphonic acid, cyclohexylimidodiphosphonic acid, norbornylimidodiphosphonic acid, dimethylimidodiphosphonic acid, diisopropylimidodiphosphonic acid, di-tert-butylimidodiphosphonic acid, diphenylimidodiphosphonic acid, di-pentafluorophenylimidodiphosphonic acid, dibenzylimidodiphosphonic acid, dicyclohexylimidodiphosphonic acid, and dinorbornylimidodiphosphonic acid. [Note: The phosphite (P+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]
[0518] O Valence Stabilizer #3: Examples of imidodiphosphonamides, hydrazidodiphosphonamides, bis(imidodiphosphonamides), bis(hydrazidodiphosphonamides), poly(imidodiphosphonamides), and poly(hydrazidodiphosphonamides) (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4include, but are not limited to imidodiphosphonamide, N-methylimidodiphosphonamide, N-isopropylimidodiphosphonamide, N-tert-butylimidodiphosphonamide, N-phenylimidodiphosphonamide, N-pentafluorophenylimidodiphosphonamide, N-benzylimidodiphosphonamide, N-cyclohexylimidodiphosphonamide, N-norbornylimidodiphosphonamide, N,N′″-dimethylimidodiphosphonamide, N,N′″-diisopropylimidodiphosphonamide, N,N′″-di-tert-butylimidodiphosphonamide, N,N′″-diphenylimidodiphosphonamide, N,N′″-di-pentafluorophenylimidodiphosphonamide, N,N′″-dibenzylimidodiphosphonamide, N,N′″-dicyclohexylimidodiphosphonamide, and N,N′″-dinorbornylimidodiphosphonamide. [Note: The phosphite (p+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]
[0519] O Valence Stabilizer #4: Examples of diphosphonamides, bis(diphosphonamides), and poly(diphosphonamides) (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diphosphonamide, N-methyldiphosphonamide, N-isopropyldiphosphonamide, N-tert-butyldiphosphonamide, N-phenyldiphosphonamide, N-pentafluorophenyldiphosphonamide, N-benzyldiphosphonamide, N-cyclohexyldiphosphonamide, N-norbornyldiphosphonamide, N,N′″-dimethyldiphosphonamide, N,N′″-diisopropyldiphosphonamide, N,N′″-di-tert-butyldiphosphonamide, N,N′″-diphenydiphosphonamide, N,N′″-di-pentafluorophenyldiphosphonamide, N,N′″-dibenzyldiphosphonamide, N,N′″-dicyclohexyldiphosphonamide, and N,N″-dinorbornyldiphosphonamide. [Note: The phosphite (P+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]
[0520] O Valence Stabilizer #5: Examples of carbonates and bis(carbonates) (O—O Bidentates and O—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: carbonate; bicarbonate; O,O-diethylcarbonate; diisopropylcarbonate; diphenylcarbonate; dibenzylcarbonate; dicyclohexylcarbonate; and dinorbornylcarbonate.
[0521] O Valence Stabilizer #6: Examples of carbazates (carbazides), bis(carbazates), and poly(carbazates) (O—OBidentates, O-O-Tridentates, and O—O Tetradentates; or possibly N—O Bidentates, N—O Tridentates, and N—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N,N′-dimethylcarbazate; N,N′-di(trifluoromethyl)carbazate; N,N′-diethylcarbazate; N,N′-diphenylcarbazate; N,N′-dibenzylcarbazate; N,N′-di(pentafluorophenyl)carbazate; N,N′-dicyclohexylcarbazate; and N,N′-dinorbornylcarbazate.
[0522] O Valence Stabilizer #7: Examples of arsonic acids, bis(arsonic acids), poly(arsonic acids), and derivatives thereof (O—O Bidentates, O—O Tridentates, O—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: arsonic acid, O-phenylarsonic acid, O-benzylarsonic acid, O-cyclohexylarsonic acid, O-norbornylarsonic acid, O,O-diphenylarsonic acid, O,O-dibenzylarsonic acid, O,O-dicyclohexylarsonic acid, O,O-dinorbornylarsonic acid; and aminophenylarsonic acids.
[0523] O Valence Stabilizer #8: Examples of alkyl- and aryl-borates and bis(borates) (O—O Bidentates and O—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: triethyl borate; diisopropyl borate; diphenyl borate; dibenzyl borate; dicyclohexyl borate; and dinorbornyl borate.
[0524] O Valence Stabilizer #9: Examples of alkyl- and aryl-boronates and bis(boronates) (O—O Bidentates and O—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diethyl boronate; diisopropyl boronate; diphenyl boronate; dibenzyl boronate; dicyclohexyl boronate; and dinorbornyl boronate. [Note: boronates tend to stabilize lower oxidation states in metal ions.]
[0525] O Valence Stabilizer #10: Examples of phosphine P-oxides and amino-substituted phosphine oxides (O Monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: trimethylphosphine oxide (TMPO); triethylphosphine oxide (TEPO); triphenylphosphine oxide (TPhPO); tribenzylphosphine oxide (TBzPO); tricyclohexylphosphine oxide (TcHxPO); and trinorbornylphosphine oxide for phosphine P-oxides; and hexamethylphosphoramide (HMPA); trimorpholinophosphine oxide (TMrPO); tripiperidinophosphine oxide; tripyrrolidinophosphine oxide; and tri(cyclohexylamino)phosphine oxide for amino-substituted phosphine oxides.
[0526] O Valence Stabilizer #11: Examples of arsine As-oxides and amino-substituted arsine oxides (O Monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: trimethylarsine oxide (TMAsO); triethylarsine oxide (TEAsO); triphenylarsine oxide (TPhAsO); tribenzylarsine oxide (TBzAsO); tricyclohexylarsine oxide (TcHxAsO); and trinorbornylarsine oxide for arsine As-oxides; and hexamethylarsonamide; trimorpholinoarsine oxide; tripiperidinoarsine oxide; tripyrrolidinoarsine oxide; and tri(cyclohexylamino)arsine oxide for amino-substituted arsine oxides.
[0527] O Valence Stabilizer #12a: Examples of 5-membered heterocyclic rings containing one oxygen atom (O monodentate) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: furan, dihydrofuran, oxazole, isoxazole, oxadiazole, oxatriazole, oxathiole, benzofuran, benzodihydrofuran, benzoxazole, benzisoxazole, benzoxadiazole (benzofurazan), dibenzofuran, dibenzoxazole, dibenzisoxazole, naphthofuran, naphthoxazole, naphthisoxazole, and naphthoxadiazole.
[0528] O Valence Stabilizer #12b: Examples of 5-membered heterocyclic rings containing two oxygen atoms (O monodentate or O—O bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dioxolane, benzodioxolane, and naphthodioxolane.
[0529] O Valence Stabilizer #13a: Examples of 6-membered heterocyclic rings containing one oxygen atom (O monodentate) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dihydropyran, pyran, oxazine, oxadiazine, oxatriazine, oxathiin, benzopyran, benzoxazine, benzoxadiazine, dibenzopyran, naphthopyran, naphthoxazine, and naphthoxadiazine.
[0530] O Valence Stabilizer #13b: Examples of 6-membered heterocyclic rings containing two oxygen atoms (O monodentate or O—O bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dihydrodioxane, dioxane, benzodioxane, dibenzodioxane, and naphthodioxane.
[0531] O Valence Stabilizer #14a: Examples of 5-membered heterocyclic rings containing one oxygen atom and having at least one additional oxygen atom binding site not contained in a ring (O monodentates, O—O bidentates, O—O tridentates, O—O tetradentates, or O—O hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2,5-dihydroxy-2,5-dihydrofuran; 2,5-bis(hydroxymethyl)-2,5-dihydrofuran; 2,5-bis(2-hydroxyphenyl)-2,5-dihydrofuran; 2,5-dihydroxyfuran; 2,5-bis(hydroxymethyl)furan; and 2,5-bis(2-hydroxyphenyl)furan.
[0532] O Valence Stabilizer #14b: Examples of 5-membered heterocyclic rings containing two oxygen atoms and having at least one additional oxygen atom binding site not contained in a ring (O monodentates, O—O bidentates, O—O tridentates, O—O tetradentates, or O—O hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-hydroxy-1,3-dioxolane; 2-hydroxymethyl)-1,3-dioxolane; 4,5-dihydroxy-1,3-dioxolane; 4,5-bis(2-hydroxyphenyl)-1,3-dioxolane; 2-hydroxybenzodioxolane; and 7-hydroxybenzodioxolane.
[0533] O Valence Stabilizer #15a: Examples of 6-membered heterocyclic rings containing one oxygen atom and having at least one additional oxygen atom binding site not contained in a ring (O monodentates, O—O bidentates, O—O tridentates, O—O tetradentates, or O—O hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2,6-dihydroxy-2,5-dihydropyran; 2,6-bis(hydroxymethyl)-2,5-dihydropyran; 2,6-bis(2-hydroxyphenyl)-2,5-dihydropyran; 2,6-dihydroxypyran; 2,6-bis(hydroxymethyl)pyran; 2,6-bis(2-hydroxyphenyl)pyran; 2-hydroxy-1-benzopyran; 8-hydroxy-1-benzopyran; and 1,9-dihydroxydibenzopyran.
[0534] O Valence Stabilizer #15b: Examples of 6-membered heterocyclic rings containing two oxygen atoms and having at least one additional oxygen atom binding site not contained in a ring (O monodentates, O—O bidentates, O—O tridentates, O—O tetradentates, or O—O hexadentates) that meet the requirements for use as “narrow band”.valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-hydroxy-1,4-dioxane; 2,6-dihydroxy-1,4-dioxane; 2,6-bis(2-hydroxyphenyl)-1,4-dioxane; 2,3-dihydroxy-1,4-benzodioxane; 5,8-dihydroxy-1,4-benzodioxane; 1,8-dihydroxydibenzodioxane; and 1,4,5,8-tetrahydroxydibenzodioxane.
[0535] O Valence Stabilizer #16a: Examples of 5-membered heterocyclic rings containing one oxygen atom and having at least one additional oxygen atom binding site contained in a ring (O monodentates, O—O bidentates, O—O tridentates, O—O tetradentates, or O—O hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2,2′-bi-2,5-dihydrofuran; 2,2′,2″-tri-2,5-dihydrofuran; 2,2′-bifuran; 2,2′,2″-trifuran; 1,1′-bis(dibenzofuran); and polyfurans.
[0536] O Valence Stabilizer #16b: Examples of 5-membered heterocyclic rings containing two oxygen atoms and having at least one additional oxygen atom binding site contained in a ring (O monodentates, O—O bidentates, O—O tridentates, O—O tetradentates, or O—O hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2,2′-bi-1,3-dioxolane; 4,4′-bi-1,3-dioxolane; 7,7′-bi-1,2-benzodioxolane; and 3,3′-bi-1,2-benzodioxolane.
[0537] O Valence Stabilizer #17a: Examples of 6-membered heterocyclic rings containing one oxygen atom and having at least one additional oxygen atom binding site contained in a ring (O monodentates, O—O bidentates, O—O tridentates, O—O tetradentates, or O—O hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2,2′-bi-2,5-dihydropyran; 2,2′,2″-tri-2,5-dihydropyran; 2,2′-bipyran; 2,2′,2″-tripyran; and 1,1′-bis(dibenzopyran).
[0538] O Valence Stabilizer #17b: Examples of 6-membered heterocyclic rings containing one oxygen atom and having at least one additional oxygen atom binding site contained in a ring (O monodentates, O—O bidentates, O—O tridentates, O—O tetradentates, or O—O hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2,2′-bi-1,4-dioxane; 2,2′-bi-1,3-dioxane; 5,5′-bi-1,4-benzodioxane; and 2,2′-bi-1,3-benzodioxane.
[0539] O Valence Stabilizer #18a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of oxygen (usually ester or hydroxyl groups) and are not contained in component heterocyclic rings (O—O Bidentates, O—O Tridentates, O—O Tetradentates, and O—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 8-crown-4; 10-crown-4; 12-crown-4; 14-crown-4; 16-crown-4; 18-crown-4; 20-crown-4; dibenzo-8-crown-4; dibenzo-10-crown-4; dibenzo-12-crown-4; dibenzo-14-crown-4; dibenzo-16-crown-4; dibenzo-18-crown-4; dibenzo-20-crown-4; tetrabenzo-8-crown-4; tetrabenzo-10-crown-4; tetrabenzo-12-crown-4; tetrabenzo-14-crown-4; tetrabenzo-16-crown-4; tetrabenzo-18-crown-4; and tetrabenzo-20-crown-4.
[0540] O Valence Stabilizer #18b: Examples of five-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of oxygen (usually ester or hydroxyl groups) and are not contained in component heterocyclic rings (O—O Bidentates, O—O Tridentates, O—O Tetradentates, and O—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 10-crown-5; 15-crown-5; 20-crown-5; 25-crown-5; pentabenzo-10-crown-5; pentabenzo-15-crown-5; pentabenzo-20-crown-5; and pentabenzo-25-crown-5.
[0541] O Valence Stabilizer #18c: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of oxygen (usually ester or hydroxyl groups) and are not contained in component heterocyclic rings (O—O Bidentates, O—O Tridentates, O—O Tetradentates, and O—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 12-crown-6; 18-crown-6; 24-crown-6; 30-crown-6; 36-crown-6; tribenzo-12-crown-6; tribenzo-18-crown-6; tribenzo-24-crown-6; tribenzo-30-crown-6; tribenzo-36-crown-6; hexabenzo-12-crown-6; hexabenzo-18-crown-6; hexabenzo-24-crown-6; hexabenzo-30-crown-6; and hexabenzo-36-crown-6.
[0542] O Valence Stabilizer #18d: Examples of seven-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of oxygen (usually ester or hydroxyl groups) and are not contained in component heterocyclic rings (O—O Bidentates, O—O Tridentates, O—O Tetradentates, and O—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 14-crown-7; 21-crown-7; 28-crown-7; 35-crown-7; heptabenzo-14-crown-7; heptabenzo-21-crown-7; heptabenzo-28-crown-7; and heptabenzo-35-crown-7.
[0543] O Valence Stabilizer #18e: Examples of eight-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of oxygen (usually ester or hydroxyl groups) and are not contained in component heterocyclic rings (O—O Bidentates, O—O Tridentates, O—O Tetradentates, and O—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 16-crown-8; 24-crown-8; 32-crown-8; 40-crown-8; 48-crown-8; tetrabenzo-16-crown-8; tetrabenzo-24-crown-8; tetrabenzo-32-crown-8; tetrabenzo-40-crown-8; tetrabenzo-48-crown-8; octabenzo-16-crown-8; octabenzo-24-crown-8; octabenzo-32-crown-8; octabenzo-40-crown-8; and octabenzo-48-crown-8.
[0544] O Valence Stabilizer #18f: Examples of ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of oxygen (usually ester or hydroxyl groups) and are not contained in component heterocyclic rings (O—O Bidentates, O—O Tridentates, O—O Tetradentates, and O—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 20-crown-10; 30-crown-10; 40-crown-10; 50-crown-10; pentabenzo-20-crown-10; pentabenzo-30-crown-10; pentabenzo-40-crown-10; and pentabenzo-50-crown-10.
[0545] O Valence Stabilizer #19: Examples of four-, five-, six-, seven-, eight-, and ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of oxygen and are contained in component 5-membered heterocyclic rings (O—O Bidentates, O-O Tridentates, O—O Tetradentates, and O—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: tetrafurans, tetrabenzofurans; pentafurans; pentabenzofurans; hexafurans; hexabenzofurans; heptafurans; heptabenzofurans; octafurans; octabenzofurans; decafurans; and decabenzofurans.
[0546] O Valence Stabilizer #20: Examples of four-, five-, six-, seven-, eight-, and ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of oxygen and are contained in component 6-membered heterocyclic rings (O—O Bidentates, O—O Tridentates, O—O Tetradentates, and O—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: tetrapyrans, tetrabenzopyrans; pentapyrans; pentabenzopyans; hexapyans; hexabenzopyans; heptapyans; heptabenzopyans; octapyans; octabenzopyans; decapyans; and decabenzopyans.
[0547] N—S Valence Stabilizer #1: Examples of thioimidates, dithioimidates, polythioimidates, and derivatives of thioimidic acid (N—S bidentates and N—S tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: S-methyl formathioimidate; S-ethyl formathioimidate; S-methyl acetathioimidate; S-ethyl acetathioimidate; S-methyl benzthioimidate; S-ethyl benzthioimidate; S-methyl cyclohexylthioimidate; S-ethyl cyclohexylthioimidate; S-methyl pentafluorobenzthioimidate; S-ethyl pentafluorobenzthioimidate; S-methyl 2-pyridylthioimidate; S-ethyl 2-pyridylthioimidate; S,S′-dimethyl benzdithioimidate; S,S′-dimethyl tetrafluorobenzdithioimidate; 2-iminothiolane; and 2-iminotetrahydrothiopyran. [Note: Many thioimidate complexes are decomposed by water, but their stability can be enhanced through the use of fluorinated solubility control anions (e.g. PF6−).]
[0548] N—S Valence Stabilizer #2: Examples of thioguanylureas, guanidinothioureas, bis(thioguanylureas), bis(guanidinothioureas, pQly(thioguanylureas), and poly(guanidinothioureas) (N—S Bidentates and N—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: thioguanylurea (amidinothiourea); guanidinothiourea; methylthioguanylurea; ethylthioguanylurea; isopropylthioguanylurea; butylthioguanylurea; benzylthioguanylurea; phenylthioguanylurea; tolylthioguanylurea; naphthylthioguanylurea; cyclohexylthioguanylurea; norbornylthioguanylurea; adamantylthioguanylurea; dimethylthioguanylurea; diethylthioguanylurea; diisopropylthioguanylurea; dibutylthioguanylurea; dibenzylthioguanylurea; diphenylthioguanylurea; ditolylthioguanylurea; dinaphthylthioguanylurea; dicyclohexylthioguanylurea; dinorbornylthioguanylurea; diadamantylthioguanylurea; ethylenebis(thioguanylurea); propylenebis(thioguanylurea); phenylenebis(thioguanylurea); piperazinebis(thioguanylurea); oxalylbis(thioguanylurea); malonylbis(thioguanylurea); succinylbis(thioguanylurea); and phthalylbis(thioguanylurea). [Note: thioguanylureas generally tend to favor lower oxidation states in complexed metals.]
[0549] N—S Valence Stabilizer #3: Examples of amidinothioamides, guanidinothioamides, bis(amidinothioamides), bis(guanidinothioamides), poly(amidinothioamides), and poly(guanidinothioamides) (including both N-amidinothioamides and 2-amidinothioacetamides) (N—S Bidentates, N—S Tridentates, and N—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: amidinothioacetamide; guanidinothioamide, amidinothiopropanamide; amidinothiobutanamide; amidinothiobenzamide; amidinothiotoluamide; amidinothiocyclohexamide; N-methylamidinothioacetamide; N-ethylamidinothiopropanamide; N-propylamidinothiobutanamide; N-phenylamidinothiobenzamide; N-tolylamidinothiotoluamide; N-cyclohexylamidinothiocyclohexamide; bis(amidinothiooxamide); bis(amidinothiomalonamide); bis(amidinothiosuccinamide); bis(amidinothiophthalamide); 2-amidinothioacetamide (thiomalonamamidine); N-methyl-2-amidinothioacetamide; N-ethyl-2-amidinothioacetamide; N-phenyl-2-amidinothioacetamide; N-benzyl-2-amidinothioacetamide; N-cyclohexyl-2-amidinothioacetamide; N,N′-dimethyl-2-amidinothioacetamide; N,N′-diethyl-2-amidinothioacetamide; N,N′-diphenyl-2-amidinothioacetamide; N,N′-dibenzyl-2-amidinothioacetamide; and N,N′-dicyclohexyl-2-amidinothioacetamide. [Note: amidinothioamides generally tend to favor lower oxidation states in complexed metals.]
[0550] N—S Valence Stabilizer #4: Examples of imidoylthioamides, bis(imidoylthioamides), and poly(imidoylthioamides); (N—S Bidentates, N—S Tridentates, and N—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: acetimidoylthioacetamide; acetimidoylthiopropanamide; acetimidoylthiobutanamide; acetimidoylthiobenzamide; acetimidolylthiotoluamide; acetimidoylthiocyclohexamide; propimidoylthiopropanamide; butimidoylthiobutanamide; benzimidoylthiobenzamide; ethylenebis(acetimidoylthioacetamide); propylenebis(acetimidoylthioacetamide); and phenylenebis(acetimidoylthioacetamide). [Note: imidoylthioamides generally tend to favor lower oxidation states in complexed metals.]
[0551] N—S Valence Stabilizer #5: Examples of thioureas, bis(thioureas), and poly(thioureas), including thiourylene complexes (N—S bidentates and N—S tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: thiourea; methylthiourea; ethylthiourea; isopropylthiourea; benzylthiourea; phenylthiourea; cyclohexylthiourea; naphthylthiourea (ntu); biphenylthiourea; norbornylthiourea; adamantylthiourea; N,N′-dimethylthiourea; N,N′-diethylthiourea; N,N′-diisopropylthiourea; N,N′-dibenzylthiourea; N,N′-dicyclohexylthiourea; N,N′-dinapthylthiourea; N,N′-dibiphenylthiourea; N,N′-dinorbornylthiourea; N,N′-diadamantylthiourea; tetramethylthiourea; ethylenethiourea (2-imidazolidinethione)(etu); 4,5-dihydroxy-2-imidazolinethione (dhetu); propylenethiourea; N-(thiazol-2-yl)thiourea; diphenylphosphinothioyl thioureas; allylthiourea; N-allyl-N′-pyridylthiourea; N-allyl-N′-anisylthiourea; N-allyl-N′-naphthylthiourea; N-allyl-N′-phenylthiourea; thioglycoluril (acetylenethiourea); and bis(pyridylmethyl)thiourea. [Note: thioureas generally tend to favor lower oxidation states in complexed metals.]
[0552] N—S Valence Stabilizer #6: Examples of thiocarboxamides, bis(thiocarboxamides), and poly(thiocarboxamides), (N—S bidentates, N—S tridentates, and N—S tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: thiocarbamide (tu); thioacetamide (taa); thiopropionamide; thiobutanamide; thiobenzamide (1-pbenylthioformamide)(tba); 1-naphthylthioformamide; 1-cyclohexylthioformamide); 1-norbornylthioformamide; 1-adamantylthioformamide; N,N-dimethylthioformamide; N,N-dimethylthioacetamide; pyridine-2-thiocarboxamide (thiopicolinamide); pyrazine-2,3-dithiocarboxamide; thionicotinamide; 2-thiophenethiocarhoxamide; N N-dimethylthiobenzamide; N-ethylthiocarbamide (N-etu); tetramethylthiocarbamide (tmtu); 2-thioacetamidothiazole (tatz); and polythioacrylamides. [Note: thiocarboxamides generally tend to favor lower oxidation states in complexed metals.]
[0553] N—S Valence Stabilizer #7: Examples of imidosulfurous diamides and bis(imidosulfurous diamides) (N—S Bidentates, N—S Tridentates, and N—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N,N′-diphenylimidosulfurous diamide; N,N′-dibenzylimidosulfurous diamide; and phenylenebis(imidosulfurous diamide). [Note: These complexes tend to hydrolyze unless stabilized with a fluorinated anionic solubility control agent. The sulfite (S+4) valence of the sulfur atom makes stabilizization of high valence metal ions much more difficult, though still possible.]
[0554] N—S Valence Stabilizer #8: Examples of sulfurdiimines, bis(sulfurdiimines), and poly(sulfurdiimines) (N—S Bidentates, N—S Tridentates, and N—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N,N′-diphenylsulfurdiimine; N,N′-dibenzylsulfurdiimine; and phenylenebis(sulfurdiimine). [Note: These complexes tend to hydrolyze unless stabilized with a fluorinated anionic solubility control agent. The sulfite (S+4) valence of the sulfur atom makes stabilizization of high valence metal ions much more difficult, though still possible.]
[0555] N—S Valence Stabilizer #9: Examples of phosphonimidothioic acid, phosphonimidodithioic acid, bis(phosphonimidothioic acid); bis(phosphonimidodithioic acid), and derivatives thereof (N—S Bidentates, N—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: phosphonimidothioic acid, phosphonimidodithioic acid; O-phenylphosphonimidothioic acid; O-benzylphosphonimidothioic acid; O-cyclohexylphosphonimidothioic acid; O-norbornylphosphonimidothioic acid; S-phenylphosphonimidodithioic acid; S-benzylphosphonimidodithioic acid; S-cyclohexylphosphonimidodithioic acid; and S-norbornylphosphonimidodithioic acid. [Note: The phosphite (P+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]
[0556] N—S Valence Stabilizer #10: Examples of phosphonothioic diamides, bis(phosphonothioic diamides), and poly(phosphonothioic diamides) (N—S Bidentates and N—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: phosphonothioic diamide, phosphonothioic dihydrazide, phosphonamidothioic hydrazide, N-phenylphosphonothioic diamide, N-benzylphosphonothioic diamide, N-cyclohexylphosphonothioic diamide, and N-norbornylphosphonothioic diamide. [Note: The phosphite (P+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]
[0557] N—S Valence Stabilizer #11: Examples of phosphonamidothioic acid, phosphonamidiinidodithioic acid, bis(phosphonamidothioic acid), bis(phosphonamidimidodithioic acid), poly(phosphonamidothioic acid), and poly(phosphonamidimidodithioic acid), and derivatives thereof (N—S Bidentates and N—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: phosphonamidothioic acid, phosphonamidimidodithioic acid, phosphonohydrazidodithioic acid, phosphonohydrazidothioic acid, S-phenylphosphonamidimidodithioic acid, S-benzylphosphonamidimidodithioic acid, S-cyclohexylphosphonamidimidodithioic acid, and S-norbornylphosphonamidimidodithioic acid. [Note: The phosphite (P+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]
[0558] N—S Valence Stabilizer #12: Examples of beta-aminothiones (N-substituted 3-amino-2-propenethioaldehydes), bis(beta-aminothiones), and poly(beta-aminothiones) (N—S Bidentates and N—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 4-methylamino-3-penten-2-thione; 4-ethylamino-3-penten-2-thione; 4-isopropyl amino-3-penten-2-thione; 4-phenylamino-3-penten-2-thione; 4-naphthylamino-3-penten-2-thione; 4-cyclohexylamino-3-penten-2-thione; 4-norbornylamino-3-penten-2-thione; 4-hydroxyamino-3-penten-2-thione; 3-methylamino-1-phenyl-2-butenethioaldehydel; 3-ethylamino-1-phenyl-2-butenethioaldehyde; 3-isopropylamino-1-phenyl-2-butenethioaldehyde; 3-phenylamino-1-phenyl-2-butenethioaldehyde; 3-naphthylamino-1-phenyl-2-butenethioaldehyde; 3-cyclohexylamino-1-phenyl-2-butenethioaldehyde; 3-norbornylamino-1-phenyl-2-butenethioaldehyde; 3-hydroxyamino-1-phenyl-2-butenethioaldehyde; 3-phenylamino-1,3-diphenyl-2-propenethioaldehyde; 3-cyclohexylamino-1,3-dicyclohexyl-2-propenethioaldehyde; and 3-norbornylamino-1,3-dinorbornyl-2-propenethioaldehyde.
[0559] N—S Valence Stabilizer #13: Examples of 3-aminothioacrylamides (3-amino-2-thiopropenamides), 3,3-diaminothioacrylamides, bis(3-aminothioacrylamides), bis(3,3-diaminothioacrylamides), poly(3-aminothioacrylamides), and poly(3,3-diaminothioacrylamides) (N—S Bidentates and N—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 3-methylaminothioacryl amide; 3-ethylaminothioacrylamide, 3-i sopropyl aminothioacryl amide, 3-phenylaminothioacrylamide; 3-naphthylaminothioacrylamide; 3-cyclohexylaminothioacrylamide; 3-norbornylaminothioacrylamide; 3-hydroxyaminothioacrylamide; N—ethyl-3-methylaminothioacrylamide; N-ethyl-3-ethylaminothioacrylamide, N-isopropyl-3-isopropylaminothioacrylamide, N-phenyl-3-phenylaminothioacrylamide; N-naphthyl-3-naphthylaminothioacrylamide; N-cyclohexyl-3-cyclohexylaminothioacrylamide; N-norbornyl-3-norbornylaminothioacrylamide; 3-amino-3-methylaminothioacrylamide; 3-amino-3-ethylaminothioacrylamide, 3-amino-3-isopropylaminothioacrylamide, 3-amino-3-phenylaminothioacrylamide; 3-amino-3-naphthylaminothioacrylamide; 3-amino-3-cyclohexylaminothioacrylamide; 3-amino-3-norbornylaminothioacrylamide; and 3-amino-3-hydroxyaminothioacrylamide.
[0560] N—S Valence Stabilizer #14: Examples of 3-aminothioacrylic acids (3-amino-2-thiopropenoic acids), 3-mercapto-3-aminothioacrylic acids, bis(3-aminothioacrylic acids), bis(3-mercapto-3-aminothioacrylic acids), poly(3-aminothioacrylic acids), and poly(3-mercapto-3-aminothioacrylic acids), and derivatives thereof (N—S Bidentates and N—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 3-aminothioacrylic acid; 3-mercapto-3-aminothioacrylic acid; 3-methylaminothioacrylic acid; 3-ethylaminothioacrylic acid; 3-isopropylaminothioacrylic acid; 3-phenylaminothioacrylic acid; 3-naphthylaminothioacrylic acid; 3-cyclohexylaminothioacrylic acid; 3-norbornylaminothioacrylic acid; 3-hydroxyaminothioacrylic acid; methyl 3-methylaminothioacrylate; ethyl 3-ethylaminothioacrylate; isopropyl 3-isopropylaminothioacrylate; benzyl 3-phenylaminothioacrylate; naphthyl 3-naphthylaminothioacrylate; cyclohexyl 3-cyclohexylaminothioacrylate; and norbornyl 3-norbornylaminothioacryl ate.
[0561] N—S Valence Stabilizer #15: Examples of N-thioacyl benzylidenimines, bis(N-thioacyl benzylidenimines), and poly(N-thioacyl benzylidenimines) (N—S Bidentates and N—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N-thioformyl benzylidenimine, N-thioacetyl benzylidenimine; N-thiobenzoyl benzylidenimine; and N-pentafluorothiobenzoyl benzylidenimine.
[0562] N—S Valence Stabilizer #16: Examples of thiocarbonyl oximes, bis(thiocarbonyl oximes), and poly(thiocarbonyl oximes) (N—S Bidentates, N—S Tridentates, and N—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: butane-3-thione-2-one monoxime); and diphenylethane-2-thione-1-one monoxime.
[0563] N—S Valence Stabilizer #17: Examples of mercapto oximes, bis(mercapto oximes), and poly(mercapto oximes) (including 2-sulfur heterocyclic oximes) (N—S Bidentates, N—S Tridentates, N—S Tetradentates, and N—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 3-mercaptobutan-2-one oxime; 4-mercaptohexan-3-one oxime; (1,2-diphenyl-2-mercaptoethanone oxime); 1,2-di(trifluoromethyl)-2-mercaptoethanone oxime; 1,2-dicyclohexyl-2-mercaptoethanone oxime; 1,2-dinorbornyl-2-mercaptoethanone oxime; 2-mercaptobenzaldehyde oxime; 2-mercapto-1-naphthaldehyde oxime; thiophene-2-aldoxime; methyl 2-thiophenyl ketoxime; and phenyl 2-thiophenyl ketoxime.
[0564] N—S Valence Stabilizer #18: Examples of 2-nitrothiophenols (2-nitrobenzenethiols) (N—S Bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-nitrothiophenol; 2,3-dinitrothiophenol; 2,4-dinitrothiophenol; 2,5-dinitrothiophenol; 2,6-dinitrothiophenol; 1-nitro-2-naphthalenethiol; and 2-nitro-1-naphthalenethiol.
[0565] N—S Valence Stabilizer #19: Examples of 2-nitrilothiophenols (2-nitrilobenzenethiols) (N—S Bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-cyanothiophenol; 2,3-dicyanothiophenol; 2,4-dicyanothiophenol; 2,5-dicyanothiophenol; 2,6-dicyanothiophenol; 1-cyano-2-naphthalenethiol; and 2-cyano-1-naphthalenethiol.
[0566] N—S Valence Stabilizer #20: Examples of thiohydrazides, bis(thiohydrazides), and poly(thiohydrazides) (N—S Bidentates and N—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: thioformic hydrazide; thioacetic hydrazide; thiopropionic hydrazide; thiobenzoic hydrazide; thiophthalhydrazide; thiosalicylic hydrazide; thionaphthoic hydrazides; thionorbornaneacetic hydrazide; thionicotinic hydrazide; and thioisonicotinic hydrazide. [Note: Thiohydrazides prefer complexation with lower oxidation states in metal ions.]
[0567] N—S Valence Stabilizer #21: Examples of thiosemicarbazides, bis(thiosemicarbazides), and poly(thiosemicarbazides) (N—S Bidentates, N—S Tetradentates, and N—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: thiosemicarbazide (tsc); thiosemicarbazide diacetic acid (tsda); 1-methylthiosemicarbazide (1 mts); 1-ethylthiosemicarbazide; 1-isopropylthiosemicarbazide; 1-phenylthiosemicarbazide (1 pts)(cryogenine); 1-benzylthiosemicarbazide; 1-cyclohexylthiosemicarbazide; 1-norbornylthiosemicarbazide; 4-methylthiosemicarbazide (4mts); 4-ethylthiosemicarbazide; 4-isopropylthiosemicarbazide; 4-phenylthiosemicarbazide (4-pts); 4-benzylthiosemicarbazide; 4-cyclohexylthiosemicarbazide; 4-norbornylthiosemicarbazide; nicotinic thiosemicarbazide; isonicotinic thiosemicarbazide; and 4-phenyl-1-benzenesulfonyl-3-thiosemicarbazide (pbst). [Note: Thiosemicarbazides prefer complexation with lower oxidation states in metal ions.]
[0568] N—S Valence Stabilizer #22: Examples of five-, seven-, or nine-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen (usually amine or imine groups) or sulfur (usually thiols, mercaptans, or thiocarbonyls) and are not contained in component heterocyclic rings (N—S Tridentates, N—S Tetradentates, and N—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+ include, but are not limited to: triazadithiacyclodecane ([10]aneS2N3); triazadithiacycloundecane ([11]aneS2N3); triazadithiacyclododecane ([12]aneS2N3); triazadithiacyclotridecane ([13]aneS2N3); triazadithiacyclotetradecane ([14]aneS2N3); triazadithiacyclopentadecane ([15]aneS2N3); thiomorpholine; and thiazolidine.
[0569] N—S Valence Stabilizer #23: Examples of five- or seven-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen or sulfur and are contained in component heterocyclic rings (N—S Bidentates, N—S Tridentates, N—S Tetradentates, or N—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiopyrantripyridines; dithiophenetripyrroles; trithiopyrantetrapyridines; and trithiophenetetrapyrroles.
[0570] N—S Valence Stabilizer #24: Examples of five-, seven-, or nine-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen or sulfur and are contained in a combination of heterocyclic rings and amine, imine, thiol, mercapto, or thiocarbonyl groups (N—S Bidentates, N—S Tridentates, N—S Tetradentates, or N—S Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: azathiapentaphyrins; diazadithiapentaphyrins; azathiapentaphyrins; and diazadithiapentaphyrins.
[0571] N—O Valence Stabilizer #1: Examples of imidates, diimidates, polyimidates, and derivatives of imidic acid (N—O bidentates and N—O tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: O-methyl formimidate; O-ethyl formimidate; O-methyl acetimidate; O-ethyl acetimidate; O-methyl benzimidate; O-ethyl benzimidate; O-methyl cyclohexylimidate; O-ethyl cyclohexylimidate; O-methyl pentafluorobenzimidate; O-ethyl pentafluorobenzimidate; O-methyl 2-pyridylimidate; O-ethyl 2-pyridylimidate; O,O′-dimethyl benzdiimidate; O,O′-dimethyl tetrafluorobenzdiimidate; 2-iminotetrahydrofuran; and 2-iminotetrahydropyran. [Note: Most imidate complexes are decomposed by water, but their stability can be enhanced through the use of fluorinated solubility control anions (e.g. PF6−).]
[0572] N—O Valence Stabilizer #2: Examples of pseudoureas, bis(pseudoureas), and poly(pseudoureas) (N—O bidentates and N—O tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: O-methyl pseudourea; O-ethyl pseudourea; O-isopropyl pseudourea; O-benzyl pseudourea; O-cyclohexyl pseudourea; O-norbornyl pseudourea; O-pentafluorobenzyl pseudourea; N-methyl pseudourea; N-ethyl pseudourea; N-isopropyl pseudourea; N-benzyl pseudourea; N-cyclohexyl pseudourea; N-norbornyl pseudourea; and N-pentafluorobenzyl pseudourea.
[0573] N—O Valence Stabilizer #3: Examples of 2-amidinoacetates, bis(2-amidinoacetates), and poly(2-amidinoacetates) (N—O Bidentates and N—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N-methyl-2-amidinoacetate; O-methyl-2-amidinoacetate; N-benzyl-2-amidinoacetate; and O-benzyl-2-amidinoacetate. [Note: many 2-amidinoacetates tend to hydrolyze in water. This can be minimized through the use of fluorinated solubility control anions such as PF6−.]
[0574] N—O Valence Stabilizer #4: Examples of ureas, bis(ureas), and poly(ureas), including urylene complexes (N—O bidentates and N—O tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: urea; methylurea; ethylurea; isopropylurea; benzylurea; cyclohexylurea; naphthylurea; biphenylurea; norbornylurea; adamantylurea; N,N′-dimethylurea; N,N′-diethylurea; N,N′-diisopropylurea; N,N′-dibenzylurea; N,N′-dicyclohexylurea; N,N′-dinapthylurea; N,N′-dibipbenylurea; N,N′-dinorbornylurea; N,N′-diadamantylurea; ethyleneurea (2-imidazolidone); propyleneurea; glycoluril (acetyleneurea); and N,N′-bis(4-nitrophenyl)urea.
[0575] N—O Valence Stabilizer #5: Examples of phosphonimidic-acid, bis(phosphonimidic acid), poly(phosphonimidic acid), and derivatives thereof (N—O Bidentates and N—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: phosphonimidic acid; O-phenylphosphonimidic acid; O-benzylphosphonimidic acid; O-cyclohexylphosphonimidic acid; and O-norbornylphosphonimidic acid. [Note: The phosphite (P+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]
[0576] N—O Valence Stabilizer #6: Examples of phosphonamidic acid, phosphonic diamide, bis(phosphonamidic acid), bis(phosphonic diamide), poly(phosphonamidic acid), poly(phosphonic diamide), and derivatives thereof (N—O Bidentates and N—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: phosphonamidic acid, phosphonic diamide, phosphonamidic hydrazide, phosphonic dihydrazide, O-phenylphosphonamidic acid, O-benzylphosphonamidic acid, O-cyclohexylphosphonamidic acid, O-norbornylphosphonamidic acid, N-benzylphosphonic diamide, N-phenylphosphonic diamide, N-cyclohexylphosphonic diamide, and N-norbornylphosphonic diamide. [Note: The phosphite (P+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]
[0577] N—O Valence Stabilizer #7: Examples of beta-ketoamines (N-substituted 3-amino-2-propenals), bis(beta-ketoamines), and poly(beta-ketoamines) (N—O Bidentates and N—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 4-methylamino-3-penten-2-one; 4-ethylamino-3-penten-2-one; 4-isopropylamino-3-penten-2-one; 4-phenylamino-3-penten-2-one; 4-naphthylamino-3-penten-2-one; 4-cyclohexylamino-3-penten-2-one; 4-norbornylamino-3-penten-2-one; 4-hydroxyamino-3-penten-2-one; 3-methylamino-1-phenyl-2-butenal; 3-ethylamino-1-phenyl-2-butenal; 3-isopropylamino-1-phenyl-2-butenal; 3-phenylamino-1-phenyl-2-butenal; 3-naphthylamino-1-phenyl-2-butenal; 3-cyclohexylamino-1-phenyl-2-butenal; 3-norbornylamino-1-phenyl-2-butenal; 3-hydroxyamino-1-phenyl-2-butenal; 3-phenylamino-1,3-diphenyl-2-propenal; 3-cyclohexylamino-1,3-dicyclohexyl-2-propenal; 3-norbornylamino-1,3-dinorbornyl-2-propenal; 2,2′-pyridil; alpha-pyridoin; 4-aminoantipyrine (aap); beta-phenylaminopropiophenone; and polyaminoquinones (PAQs).
[0578] N—O Valence Stabilizer #8: Examples of 3-aminoacrylamides (3-amino-2-propenamides), 3,3-diaminoacrylamides, bis(3-aminoacrylamides), bis(3,3-diaminoacrylamides), poly(3-aminoacrylamides), and poly(3,3-diaminoacrylamides) (N—O Bidentates and N—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 3-methylaminoacrylamide; 3-ethylaminoacrylamide, 3-isopropylaminoacrylamide, 3-phenylaminoacrylamide; 3-naphthylaminoacrylamide; 3-cyclohexylaminoacrylamide; 3-norbornylaminoacrylamide; 3-hydroxyaminoacrylamide; N-methyl-3-methylaminoacrylamide; N-ethyl-3-ethylaminoacrylamide, N-isopropyl-3-isopropylaminoacrylamide, N-phenyl-3-phenylaminoacrylamide; N-naphthyl-3-naphthylaminoacrylamide; N-cyclohexyl-3-cyclohexylaminoacrylamide; N-norbornyl-3-norbornylaminoacrylamide; 3-amino-3-methylaminoacrylamide; 3-amino-3-ethylaminoacrylamide, 3-amino-3-isopropylaminoacrylamide, 3-amino-3-phenylaminoacrylamide; 3-amino-3-naphthylaminoacrylamide; 3-amino-3-cyclohexylaminoacrylamide; 3-amino-3-norbornylaminoacrylamide; and 3-amino-3-hydroxyaminoacrylamide.
[0579] N—O Valence Stabilizer #9: Examples of 3-aminoacrylic acids (3-amino-2-propenoic acids), 3-hydroxy-3-aminoacrylic acids, bis(3-aminoacrylic acids), bis(3-hydroxy-3-aminoacrylic acids), poly(3-aminoacrylic acids), and poly(3-hydroxy-3-aminoacrylic acids), and derivatives thereof (N—O Bidentates and N—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 3-aminoacrylic acid; 3-hydroxy-3-aminoacrylic acid; 3-methylaminoacrylic acid; 3-ethylaminoacrylic acid; 3-isopropylaminoacrylic acid; 3-phenylaininoacrylic acid; 3-naphthylaminoacrylic acid; 3-cyclohexylaminoacrylic acid; 3-norbornylaminoacrylic acid; 3-hydroxyaminoacrylic acid; methyl 3-methylaminoacrylate; ethyl 3-ethylaminoacrylate; isopropyl 3-isopropylaminoacrylate; benzyl 3-phenylaminoacrylate; naphthyl 3-naphthylaminoacrylate; cyclohexyl 3-cyclohexylaminoacrylate; and norbornyl 3-norbornyl aminoacryl ate.
[0580] N—O Valence Stabilizer #10: Examples of N-acyl benzylidenimines, bis(N-acyl benzylidenimines), and poly(N-acyl benzylidenimines) (N—O Bidentates and N—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N-formyl benzylidenimine, N-acetyl benzylidenimine; N-benzoyl benzylidenimine; and N-pentafluorobenzoyl benzylidenimine.
[0581] N—O Valence Stabilizer #11: Examples of 2-nitroanilines (N—O Bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+ include, but are not limited to: 2-nitroaniline; 2,6-dintroaniline; 2-nitrophenylenediamine; 2-nitrophenylenetriamine; 2-nitro-1-aminonaphthalene; 1-nitro-2-aminonaphthalene; nitrodiaminonaphthalene; and dipicrylamine.
[0582] N—O Valence Stabilizer #12: Examples of 2-nitrilophenols (N—O Bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-cyanophenol; 2,3-dicyanophenol; 2,4-dicyanophenol; 2,5-dicyanophenol; 2,6-dicyanophenol; 1-cyano-2-naphthol; and 2-cyano-1-naphthol. Also includes acylcyanamides.
[0583] N—O Valence Stabilizer #13: Examples of amine N-oxides and N-diazine oxides (azoxy compounds) (N—O Bidentates, N—O Tridentates, and N—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: pyridine N-oxide (pyNO or PNO); picoline N-oxide (picNO); lutidine N-oxide (lutNO or LNO); collidine N-oxide (collNO or CNO); quinoline N-oxide (QuinNO or QNO); isoquinoline N-oxide (isoQuinNO or IQNO); acridine N-oxide (AcrNO or ANO); picolinic acid N-oxide (PicANO); pyridinethiolate N-oxide (PTNO); adenine N-oxide; adenosine N-oxide; 1,10-phenanthroline mono-N-oxide (phenNO); 1,10-phenanthroline N,N-dioxide (phen2NO); bipyridyl mono-N-oxide (bipyNO); bipyridyl N,N-dioxide (bipy2NO); pyrazine mono-N-oxide (pyzNO); pyrazine N,N-dioxide (pyz2NO); pyrimidine mono-N-oxide (pymNO); pyrimidine N,N-dioxide (pym2NO); pyridazine mono-N-oxide (pdzNO); pyridazine N,N-dioxide (pdz2NO); quinoxaline mono-N-oxide (qxNO); quinoxaline N,N-dioxide (qx2NO); phenazine mono-N-oxide (phzNO); phenazine N,N-dioxide (phz2NO); 2,3-di(pyridine N-oxide)quinoxaline (dpoq); inosine N-oxide; 4,4′-bipyridine N,N-dioxide; 1-hydroxypyrazole 2-oxide; 1-hydroxyimidazole 3-oxide; 2,2′-diimidazyl 3,-3′-dioxide; imidazole N-oxides; lIhydroxyimidazole-3-N-oxides; N-benzylidine aniline N-oxide; N-(naphthylidene) aniline N-oxide; N-(hydroxybenzylidene) aniline N-oxide; and 2,2′-dibenzimidazyl 3,3′-dioxide (indigo N,N-dioxide) for amine N-oxides; and azoxybenzene; phthalazine N-oxide; benzocinnoline N-oxide; and bipyrazinyl N-oxide as N-diazine oxide examples.
[0584] N—O Valence Stabilizer #14: Examples of hydrazides, bis(hydrazides), and poly(hydrazides) (N—O Bidentates and N—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: formic hydrazide; acetic hydrazide; propionic hydrazide; benzoic hydrazide; phthalhydrazide; salicylic hydrazide; naphthoic hydrazides; norbornaneacetic hydrazide; nicotinic hydrazide; and isonicotinic hydrazide (isoniazid). [Note: Hydrazides prefer complexation with lower oxidation states in metal ions.]
[0585] N—O Valence Stabilizer #15: Examples of semicarbazides, bis(semicarbazides), and poly(semicarbazides) (N—O Bidentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: semicarbazide (sc); semicarbazide diacetic acid (sda); 1-methylsemicarbazide; 1-ethylsemicarbazide; 1-isopropylsemicarbazide; 1-phenylsemicarbazide; 1-benzylsemicarbazide; 1-cyclohexylsemicarbazide; 1-norbornylsemicarbazide; 4-methylsemicarbazide; 4-ethylsemicarbazide; 4-isopropylsemicarbazide; 4-phenylsemicarbazide; 4-benzylsemicarbazide; 4-cyclohexylsemicarbazide; 4-norbornylsemicarbazide; nicotinic semicarbazide; and isonicotinic semicarbazide. [Note: Semicarbazides prefer complexation with lower oxidation states in metal ions.]
[0586] N—O Valence Stabilizer #16: Examples of five-, seven-, or nine-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen (usually amine or imine groups) or oxygen (usually hydroxy, carboxy, or carbonyl groups) and are not contained in component heterocyclic rings (N—O Tridentates, N—O Tetradentates, and N—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+ include, but are not limited to: triazadioxacyclodecane ([10]aneO2N3); triazadioxacycloundecane ([11]aneO2N3); triazadioxacyclododecane ([12]aneO2N3); triazadioxacyclotridecane ([13]aneO2N3); triazadioxacyclotetradecane ([14]aneO2N3); and triazadioxacyclopentadecane ([15]aneO2N3).
[0587] N—O Valence Stabilizer #17: Examples of five- or seven-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen or oxygen and are contained in component heterocyclic rings (N—O Bidentates, N—O Tridentates, N—O Tetradentates, or N—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dipyrantripyridines; difurantripyrroles; tripyrantetrapyridines; and trifurantetrapyrroles.
[0588] N—O Valence Stabilizer #18: Examples of five-, seven-, or nine-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen or oxygen and are contained in a combination of heterocyclic rings and amine, imine, hydroxy, carboxy, or carbonyl groups (N—O Bidentates, N—O Tridentates, N—O Tetradentates, or N—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: azaoxapentaphyrins; diazadioxapentaphyrins; azaoxapentaphyrins; and diazadioxapentaphyrins.
[0589] S—O Valence Stabilizer #1: Examples of thiobiurets (thioimidodicarbonic diamides), thioisobiurets, thiobiureas, thiotriurets, thiotriureas, bis(thiobiurets), bis(thioisobiurets), bis(thiobiureas), poly(thiobiurets), poly(thioisobiurets), poly(thiobiureas) (S—O Bidentates, S—O Tridentates, S—O Tetradentates), and (3-formamidino thiocarbamides) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: thiobiuret, thioisobiuret, thiobiurca, thiotriuret, thiotriurea, nitrothiobiuret, dinitrothiobiuret, aminothiobiuret, diaminothiobiuret, oxythiobiuret, dioxythiobiuret, cyanothiobiuret, methylthiobiuret, ethylthiobiuret, isopropylthiobiuret, phenylthiobiuret, benzylthiobiuret, cyclohexylthiobiuret, norbornylthiobiuret, adamantylthiobiuret, dimethylthiobiuret, diethylthiobiuret, dicyclohexylthiobiuret, dinorbornylthiobiuret, and diadamantylthiobiuret.
[0590] S—O Valence Stabilizer #2: Examples of acylthioureas, aroylthioureas, thioacylureas, thioaroylureas, bis(acylthioureas), bis(aroylthioureas), bis(thioacylureas) bis(thioaroylureas), poly(thioacylthioureas), poly(thioaroylthioureas), poly(thioacylureas), and poly(thioaroylureas) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: thioformylurea, thioacetylurea, thiobenzoylurea, thiocyclohexoylurea, pentafluorothiobenzoylurea, acetylthiourea, benzoylthiourea, and cyclohexoylthiourea.
[0591] S—O Valence Stabilizer #3: Examples of thioimidodialdehydes, thiohydrazidodialdehydes (thioacyl hydrazides), bis(thioimidodialdehydes), bis(thiohydrazidodialdehydes), poly(thioimidodialdehydes), and poly(thiohydrazidodialdehydes) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: thiodiacetamide, thiodipropanamide, thiodibutanamide, thiodibenzamide, and thiodicyclohexamide.
[0592] S—O Valence Stabilizer #4: Examples of thioimidodicarbonic acids, thiohydrazidodicarbonic acids, bis(thioimidodicarbonic acids), bis(thiohydrazidodicarbonic acids), poly(thioimidodicarbonic acids), poly(thiohydrazidodicarbonic acids) and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: thioimidodicarbonic acid, thiohydrazidodicarbonic acid, O-phenylthioimidodicarbonic acid, O-benzylthioimidodicarbonic acid, O-cyclohexylthioimidodicarbonic acid, O-norbornylthioimidodicarbonic acid, O,O′-diphenylthioimidodicarbonic acid, O,O′-dibenzylthioimidodicarbonic acid, O,O′-dicyclohexylthioimidodicarbonic acid, O,O′-dinorbornylthioimidodicarbonic acid.
[0593] S—O Valence Stabilizer #5: Examples of 1,2-monothioketones (monothiolenes, monothio-alpha-ketonates), 1,2,3-monothioketones, 1,2,3-dithioketones, monothiotropolonates, ortho-monothioquinones, bis(1,2-monothioketones), and poly(1,2-monothioketones) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: monothiotropolone; 1,2-monothiobenzoquinone (o-monothioquinone); di-tert-butyl-1,2-monothiobenzoquinone; hexafluoro-1,2-monothiobenzoquinone; 1,2-monothionaphthoquinone; 9,10-monothiophenanthroquinone; monothiosquaric acid; monothiodeltic acid; monothiocroconic acid; and monothiorhodizonic acid.
[0594] S—O Valence Stabilizer #6: Examples of trithioperoxydicarbonic diamides, bis(trithioperoxydicarbonic diamides), and poly(trithioperoxydicarbonic diamides) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: trithioperoxydicarbonic diamide; N-phenyltrithioperoxydicarbonic diamide; N-benzyltrithioperoxydicarbonic diamide; N-cyclohexyltrithioperoxydicarbonic diamide; N-norbornyltrithioperoxydicarbonic diamide; N,N′-diphenyltrithioperoxydicarbonic diamide; N,N′-dibenzyltrithioperoxydicarbonic diamide; N,N′-dicyclohexyltrithioperoxydicarbonic diamide; and N,N′-dinorbornyltrithioperoxydicarbonic diamide.
[0595] S—O Valence Stabilizer #7: Examples of dithiodicarbonic acids, bis(dithiodicarbonic acids), poly(dithiodicarbonic acids), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiodicarbonic acid, O-phenyldithiodicarbonic acid, O-benzyldithiodicarbonic acid, O-cyclohexyldithiodicarbonic acid, O-norbornyldithiodicarbonic acid, O,O′-diphenyldithiodicarbonic acid, O,O′-dibenzyldithiodicarbonic acid, O,O′-dicyclohexyldithiodicarbonic acid, and O,O′-dinorbornyldithiodicarbonic acid.
[0596] S—O Valence Stabilizer #8: Examples of trithioperoxydicarbonic acids, bis(trithioperoxydicarbonic acids), poly(trithioperoxydicarbonic acids), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: -trithioperoxydicarbonic acid, O-phenyltrithioperoxydicarbonic acid; O-benzyltrithioperoxydicarbonic acid; O-cyclohexyltrithioperoxydicarbonic acid; O-norbornyltrithioperoxydicarbonic acid; O,O′-diphenyltrithioperoxydicarbonic acid; O,O′-dibenzyltrithioperoxydicarbonic acid; O,O′-dicyclohexyltrithioperoxydicarbonic acid; and O,O′-dinorbornyltrithioperoxydicarbonic acid.
[0597] S—O Valence Stabilizer #9: Examples of monothioperoxydiphosphoramides, bis(monothioperoxydiphosphoramides), and poly(monothioperoxydiphosphoramides) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: monothioperoxydiphosphoramide, N-methylmonothioperoxydiphosphoramide, N-isopropylmonothioperoxydiphosphoramide, N-tert-butylmonothioperoxydiphosphoramide, N-phenylmonothioperoxydiphosphoramide, N-pentafluorophenylmonothioperoxydiphosphoramide, N-benzylmonothioperoxydiphosphoramide, N-cyclohexylmonothioperoxydiphosphoramide, N-norbornylmonothioperoxydiphosphoramide, N,N′″-dimethylmonothioperoxydiphosphoramide, N,N′″-diisopropylmonothioperoxydiphosphoramide, N,N′″-di-tert-butylmonothioperoxydiphosphoramide, N,N′″-diphenylmonothioperoxydiphosphoramide, N,N′″-di-pentafluorophenylmonothioperoxydiphosphoramide, N,N′″-dibenzylmonothioperoxydiphosphoramide, N,N′″-dicyclohexylmonothioperoxydiphosphoramide, and N,N′″-dinorbornylmonothioperoxydiphosphoramide.
[0598] S—O Valence Stabilizer #10: Examples of monothioperoxydiphosphoric acids, bis(monothioperoxydiphosphoric acids), poly(monothioperoxydiphosphoric acids), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: monothioperoxydiphosphoric acid, methylmonothioperoxydiphosphoric acid, isopropylmonothioperoxydiphosphoric acid, tert-butylmonothioperoxydiphosphoric acid, phenylmonothioperoxydiphosphoric acid, pentafluorophenylmonothioperoxydiphosphoric acid, benzylmonothioperoxydiphosphoric acid, cyclohexylmonothioperoxydiphosphoric acid, norbornylmonothioperoxydiphosphoric acid, dimethylmonothioperoxydiphosphoric acid, diisopropylmonothioperoxydiphosphoric acid, di-tert-butylmonothioperoxydiphosphoric acid, diphenylmonothioperoxydiphosphoric acid, di-pentafluorophenylmonothioperoxydiphosphoric acid, dibenzylmonothioperoxydiphosphoric acid, dicyclohexylmonothioperoxydiphosphoric acid, and dinorbornylmonothioperoxydiphosphoric acid.
[0599] S—O Valence Stabilizer #11: Examples of monothioimidodiphosphonic acids, monothiohydrazidodiphosphonic acids, bis(monothioimidodiphosphonic acids), bis(monothiohydrazidodiphosphonic acids), poly(monothioimidodiphosphonic acids), poly(monothiohydrazidodiphosphonic acids), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: monothioimidodiphosphonic acid, methylmonothioimidodiphosphonic acid, isopropylmonothioimidodiphosphonic acid, tert-butylmonothioimidodiphosphonic acid, phenylmonothioimidodiphosphonic acid, pentafluorophenylmonothioimidodiphosphonic acid, benzylmonothioimidodiphosphonic acid, cyclohexylmonothioimidodiphosphonic acid, norbornylmonothioimidodiphosphonic acid, dimethylmonothioimidodiphosphonic acid, diisopropylmonothioimidodiphosphonic acid, di-tert-butylmonothioimidodiphosphonic acid, diphenylmonothioimidodiphosphonic acid, di-pentafluorophenylmonothioimidodiphosphonic acid, dibenzylmonothioimidodiphosphonic acid, dicyclohexylmonothioimidodiphosphonic acid, and dinorbornylmonothioimidodiphosphonic acid. [Note: The phosphite (P+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]
[0600] S—O Valence Stabilizer #12: Examples of monothioimidodiphosphonamides, monothiohydrazidodiphosphonamides, bis(monothioimidodiphosphonamides), bis(monothiohydrazidodiphosphonamides), poly(monothioimidodiphosphonamides), and poly(monothiohydrazidodiphosphonamides) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: monothioimidodiphosphonamide, N-methylmonothioimidodiphosphonamide, N-isopropylmonothioimidodiphosphonamide, N-tert-butylmonothioimidodiphosphonamide, N-phenylmonothioimidodiphosphonamide, N-pentafluorophenylmonothioimidodiphosphonamide, N-benzylmonothioimidodiphosphonamide, N-cyclohexylmonothioimidodipbosphonamide, N-norbornylmonothioimidodiphosphonamide, N,N′″-dimethylmonothioimidodiphosphonamide, N,N′″-diisopropylmonothioimidodiphosphonamide, N,N′″-di-tert-butylmonothioimidodiphosphonamide, N,N′″-diphenylmonothioimidodiphosphonamide, N,N′″-di-pentafluorophenylmonothioimidodiphosphonamide, N,N′″-dibenzylmonothioimidodiphosphonamide, N,N′″-dicyclohexylmonothioimidodiphosphonamide, and N,N′″-dinorbornylmonothioimidodiphosphonamide. [Note: The phosphite (P+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]
[0601] S—O Valence Stabilizer #13: Examples of dithiodiphosphonamides, bis(dithiodiphosphonamides), and poly(dithiodiphosphonamides) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiodiphosphonamide, N-methyldithiodiphosphonamide, N-isopropyldithiodiphosphonamide, N-tert-butyldithiodiphosphonamide, N-phenyldithiodiphosphonamide, N-pentafluorophenyldithiodiphosphonamide, N-benzyldithiodiphosphonamide, N-cyclohexyldithiodiphosphonamide, N-norbornyldithiodiphosphonamide, N,N′″-dimethyldithiodiphosphonami de, N,N′″-diisopropyldithiodiphosphonamide, N,N′″-di-tert-butyldithiodiphosphonamide, N,N′″-diphenyldithiodiphosphonamide, N,N′″-di-pentafluorophenyldithiodiphosphonamide, N,N′″-dibenzyldithiodiphosphonamide, N,N′″-dicyclohexyldithiodiphosphonamide, and N,N′″-dinorbornyldithiodiphosphonamide. [Note: The phosphite (P+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]
[0602] S—O Valence Stabilizer #14: Examples of dithiodiphosphonic acids, bis(dithiodiphosphonic acids), poly(dithiodiphosphonic acids), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiodiphosphonic acid, methyldithiodiphosphonic acid, isopropyldithiodiphosphonic acid, tert-butyldithiodiphosphonic acid, phenyldithiodiphosphonic acid, pentafluorophenyldithiodiphosphonic acid, benzyldthiodiphosphonic acid, cyclohexyldithiodiphosphonic acid norbornyldithiodiphosphonic acid, dimethyldithiodiphosphonic acid, diisopropyldiothiodiphosphonic acid, di-tert-butyldithiodiphosphonic acid, diphenyldithiodiphosphonic acid, di-pentafluorophenyldithiodiphosphonic acid, dibenzyldithiodiphosphonic acid, dicyclohexyldithiodiphosphonic acid, and dinorbornyldithiodiphosphoric acid. [Note: The phosphite (P+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]
[0603] S—O Valence Stabilizer #15: Examples of monothioperoxydiphosphonamides, bis(monothioperoxydiphosphonamides), and poly(monothioperoxydiphosphonamides) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: monothioperoxydiphosphonamide, N-methylmonothioperoxydiphosphonamide, N-isopropylmonothioperoxydiphosphonamide, N-tert-butylmonothioperoxydiphosphonamide, N-phenylmonothioperoxydiphosphonamide, N-pentafluorophenylmonothioperoxydiphosphonamide, N-benzylmonothioperoxydiphosphonamide, N-cyclohexylmonothioperoxydiphosphonamide, N-norbornylmonothioperoxydiphosphonamide, N,N′″-dimethylmonothioperoxydiphosphonamide, N,N′″-diisopropylmonothioperoxydiphosphonamide, N,N′″-di-tert-butylmonothioperoxydiphosphonamide, N,N′″-diphenylmonothioperoxydiphosphonamide, N,N′″-di-pentafluorophenylmonothioperoxydiphosphonamide, N,N′″-dibenzylmonothioperoxydiphosphonamide, N,N′″-dicyclohexylmonothioperoxydiphosphonamide, and N,N′″-dinorbornylmonothioperoxydiphosphonamide. [Note: The phosphite (p+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]
[0604] S—O Valence Stabilizer #16: Examples of monothioperoxydiphosphonic acids, bis(monothioperoxydiphosphonic acids), poly(monothioperoxydiphosphonic acids), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: monothioperoxydiphosphonic acid, methylmonothioperoxydiphosphonic acid, isopropylmonothiopcroxydiphosphonic acid, tert-butylmonothioperoxydiphosphonic acid, phenylmonothioperoxydiphosphonic acid, pentafluorophenylmonothioperoxydiphosphonic acid, benzylmonothioperoxydiphosphonic acid, cyclohexylmonothioperoxydiphosphonic acid, norbornylmonothioperoxydiphosphonic acid, dimethylmonothioperoxydiphosphonic acid, diisopropylmonothioperoxydiphosphonic acid, di-tert-butylmonothioperoxydiphosphonic acid, diphenylmonothioperoxydiphosphonic acid, di-pentafluorophenylmonothioperoxydiphosphonic acid, dibenzylmonothioperoxydiphosphonic acid, dicyclohexylmonothioperoxydiphosphonic acid, and dinorbornylmonothioperoxydiphosphonic acid. [Note: The phosphite (P+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]
[0605] S—O Valence Stabilizer #17: Examples of monothiophosphoric acids (phosphorothioic acids), bis(monothiophosphoric acids), poly(monothiophosphoric acids), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: monothiophosphoric acid, O-phenylmonothiophosphoric acid, O-benzylmonothiophosphoric acid, O-cyclohexylmonothiophosphoric acid, O-norbornylmonothiophosphoric acid, O,O-diphenylmonothophosphoric acid, O,O-dibenzylmonothiophosphoric acid, O,O-dicyclohexylmonothiophosphoric acid, and O,O-dinorbornylmonothiophosphoric acid.
[0606] S—O Valence Stabilizer #18: Examples of phosphoro(dithioperoxoic) acids, bis[phosphoro(dithioperoxoic) acids], poly[phosphoro(dithioperoxoic) acids], and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: phosphoro(dithioperoxoic) acid, O-phenylphosphoro(dithioperoxoic) acid, O-benzylphosphoro(dithioperoxoic) acid, O-cyclohexylphosphoro(dithioperoxoic) acid, O-norbornylphosphoro(dithioperoxoic) acid, O,O-diphenylphosphoro(dithioperoxoic) acid, O,O-dibenzylphosphoro(dithioperoxoic) acid, O,O-dicyclohexylphosphoro(dithioperoxoic) acid, and O,O-dinorbornylphosphoro(dithioperoxoic) acid.
[0607] S—O Valence Stabilizer #19: Examples of monothiophosphonic Acids (phosphonothioic acids), bis(monothiophosphonic acids), poly(monothiophosphonic acids), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: monothiophosphonic acid, O-phenylmonothiophosphonic acid, O-benzylmonothiophosphonic acid, &bgr;-cyclohexylmonothiophosphonic acid, O-norbornylmonothiophosphonic acid, O,P-diphenylmonothiophosphonic acid, O,P-dibenzylmonothiophosphonic acid, O,P-dicyclohexylmonothiophosphonic acid, and O,P-dinorbornylmonothiophosphonic acid. [Note: The phosphite (P+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]
[0608] S—O Valence Stabilizer #20: Examples of phosphono(dithioperoxoic) acids, bis[phosphono(dithioperoxoic) acids], poly[phosphono(dithioperoxoic) acids], and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: phosphono(dithioperoxoic) acid, O-phenylphosphono(dithioperoxoic) acid, O-benzylphosphono(dithioperoxoic) acid, O-cyclohexylphosphono(dithioperoxoic) acid, O-norbornylphosphono(dithioperoxoic) acid, O,P-diphenylphosphono(dithioperoxoic) acid, O,P-dibenzylphosphono(dithioperoxoic) acid, O,P-dicyclohexylphosphono(dithioperoxoic) acid, and O,P-dinorbornylphosphono(dithioperoxoic) acid. [Note: The phosphite (P+3) valence of the phosphorus atom makes stabilizization of high valence metal ions much more difficult, though still possible.]
[0609] S—O Valence Stabilizer #21: Examples of beta-hydroxythioketones, beta-hydroxythioaldehydes, bis(beta-hydroxythioketones), bis(beta-hydroxythioaldehydes), poly(beta-hydroxythioketones), and poly(beta-hydroxythioaldehydes) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 4-hydroxypentan-2-thione; 1,3-diphenyl-3-hydroxypropanethioaldehyde; 1,3-dibenzyl-3-hydroxypropanethioaldehyde; 1,3-dicyclohexyl-3-hydroxypropanethioaldehyde; 1,3-dinorbornyl-3-hydroxypropanethioaldehyde; 1,3-di(2-thienyl)-3-hydroxypropanethioaldehyde; 1,3-di(2-furyl)-3-hydroxypropanethioaldehyde; 1-hydroxythioacetophenone; and beta-hydroxythiobenzophenone.
[0610] S—O Valence Stabilizer #22: Examples of beta-mercaptoketones, beta-mercaptoaldehydes, bis(beta-mercaptoketones), bis(beta-mercaptoaldehydes), poly(beta-mercaptoketones), and poly(beta-mercaptoaldehydes) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 4-mercaptopentan-2-one; 1,3-diphenyl-3-mercaptopropanal; 1,3-dibenzyl-3-mercaptopropanal; 1,3-dicyclohexyl-3-mercaptopropanal; 1,3-dinorbornyl-3-mercaptopropanal; 1,3-di(2-thienyl)-3-mercaptopropanal; 1,3-di(2-furyl)-3-mercaptopropanal; 3-mercapto-1,5-pentanedialdehyde; o-mercaptoacetophenone; 5-mercapto-1,4-naphthoquinone; 1-mercaptoacridone; 1-mercaptoanthraquinone; 1,8-dimercaptoanthraquinone; and beta-mercaptobenzophenone.
[0611] S—O Valence Stabilizer #23: Examples of N-(aminomethylol)thioureas [N-(aminohydroxymethyl)thioureas], bis[N-(aminomethylol)thioureas], and poly[N-(aminomethylol)thioureas] (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N′-(aminohydroxymethyl)thiourea; N,N″-dimethyl-N′-(aminohydroxymethyl)thiourea; N,N′-diethyl-N′-(aminohydroxymethyl)thiourea; N,N″-isopropyl-N′-(aminohydroxymethyl)thiourea; N,N″-diphenyl-N′-(aminohydroxymethyl)thiourea; N,N″-dibenzyl-N′-(aminohydroxymethyl)thiourea; N,N″-dicyclohexyl-N′-(aminohydroxymethyl)thiourea; and N,N″-dinorbornyl-N′-(aminohydroxymethyl)thiourea.
[0612] S—O Valence Stabilizer #24: Examples of N-(aminomethylthiol)ureas [N-(aminomercaptomethyl)ureas], bis[N-(aminomethylthiol)ureas], and poly[N-(aminomethylthiol)ureas] (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N′-(aminomercaptomethyl)urea; N,N′-dimethyl-N′-(aminomercaptomethyl)urea; N,N′-diethyl-N′-(aminomercaptomethyl)urea; N,N″-isopropyl-N′-(aminomercaptomethyl)urea; N,N″-diphenyl-N′-(aminomercaptomethyl)urea; N,N″-dibenzyl-N′-(aminomercaptomethyl)urea; N,N″-dicyclohexyl-N′-(aminomercaptomethyl)urea; and N,N″-dinorbornyl-N′-(aminomercaptomethyl)urea.
[0613] S—O Valence Stabilizer #25: Examples of monotbiooxamides, bis(monothiooxamides), and poly(monothiooxamides) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: monothiooxamide, N-methylthiooxamide; N-ethylthiooxamide; N-isopropylthiooxamide; N-phenylthiooxamide; N-benzylthiooxamide; N-cyclohexylthiooxamide; N-norbornylthiooxamide; N,N′-dimethylthiooxamide; N,N′-diethylthiooxamide; N,N′-diisopropylthiooxamide; N,N′-diphenylthiooxamide; N,N′-dibenzylthiooxamide; N,N′-dicyclohexylthiooxamide; and N,N′-dinorbornylthiooxamide.
[0614] S—O Valence Stabilizer #26: Examples of beta-mercapto carboxylic acids, bis(beta-mercapto carboxylic acids), poly(beta-mcrcapto carboxylic acids), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: methyl 3-mercaptopropanoate; methyl 3-mercaptobutanoate; ethyl 3-mercaptobutanoate; phenyl 3-mercaptobutanoate; cyclohexyl 3-mercaptobutanoate; norbornyl 3-mercaptobutanoate; methyl beta-mercaptohydrocinnamate; ethyl beta-mercaptohydrocinnamate; phenyl beta-mercaptohydrocinnamate; methyl o-mercaptobenzoate; ethyl o-mercaptobenzoate; phenyl o-mercaptobenzoate; cyclohexyl o-mercaptobenzoate; (2-benzothiazolylthio) succinic acid (mtbs); norbornyl o-mercaptobenzoate; and 3-[(benzothiazol-2-yl)thio]propionic acid.
[0615] S—O Valence Stabilizer #27: Examples of beta-mercapto thiocarboxylic acids, bis(beta-mercapto thiocarboxylic acids), poly(beta-mercapto thiocarboxylic acids), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: methyl 3-mercaptothiobutanoate; ethyl 3-mercaptothiobutanoate; phenyl 3-mercaptothiobutanoate; cyclohexyl 3-mercaptothiobutanoate; norbornyl 3-mercaptothiobutanoate; methyl beta-mercaptothiocinnamate; ethyl beta-mercaptothiocinnamate; phenyl beta-mercaptothiocinnamate; methyl o-mercaptothiobenzoate; ethyl o-mercaptothiobenzoate; phenyl o-mercaptothiobenzoate; cyclohexyl o-mercaptothiobenzoate; norbornyl o-mercaptothiobenzoate; and (alkylthio)oxoethyl alkyl(aryl) disulfides.
[0616] S—O Valence Stabilizer #28: Examples of beta-hydroxy thiocarboxylic acids, bis(beta-hydroxy thiocarboxylic acids), poly(beta-hydroxy thiocarboxylic acids), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: methyl 3-hydroxythiobutanoate; ethyl 3-hydroxythiobutanoate; phenyl 3-hydroxythiobutanoate; cyclohexyl 3-hydroxythiobutanoate; norbornyl 3-hydroxythiobutanoate; methyl beta-hydroxythiocinnamate; ethyl beta-hydroxythiocinnamate; phenyl beta-hydroxythiocinnamate; methyl o-hydroxythiobenzoate; ethyl o-hydroxythiobenzoate; phenyl o-hydroxythiobenzoate; cyclohexyl o-hydroxythiobenzoate; and norbornyl o-hydroxythiobenzoate.
[0617] S—O Valence Stabilizer #29: Examples of beta-mercapto carboxamides, bis(beta-mercapto carboxamides), poly(beta-mercapto carboxamides), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N-methyl 3-mercaptobutanamide; N-ethyl 3-mercaptobutanamide; N-phenyl 3-mercaptobutanamide; N-cyclohexyl 3-mercaptobutanamide; N-norbornyl 3-mercaptobutanamide; N-methyl o-mercaptobenzamide; N-ethyl o-mercaptobenzamide; N-phenyl o-mercaptobenzamide; N-cyclohexyl o-mercaptobenzamide; and N-norbornyl o-mercaptobenzamide.
[0618] S—O Valence Stabilizer #30: Examples of S-alkylthiocarboxylic Acids, S-arylthiocarboxylic Acids, and S,S-thiobiscarboxylic Acids (S—O Bidentates and S—O Tridentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: (methylthio)acetic acid; (methylthio)benzoic acid; (methylthio)nicotinic acid; (methylthio)napthoic acid; (phenylthio)acetic acid; (phenylthio)benzoic acid; (phenylthio)naphthoic acid; (norbornylthio)acetic acid; (norbornylthio)benzoic acid; (norbornylthio)napthoic acid; thiobisacetic acid; thiobisbenzoic acid; and thiobisnapthoic acid.
[0619] S—O Valence Stabilizer #31: Examples of S-alkyldisulfidocarboxylic acids, S-aryldisulfidocarboxylic acids, and S,S′-disulfidobiscarboxylic acids (S—O Bidentates and S—O Tridentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: (methyldisulfido)acetic acid; (methyldisulfido)benzoic acid; (methyldisulfido)nicotinic acid; (methyldisulfido)napthoic acid; (phenyldisulfido)acetic acid; (phenyldisulfido)benzoic acid; (phenyldisulfido)naphthoic acid; (norbornyldisulfido)acetic acid; (norbornyldisulfido)benzoic acid; (norbornyldisulfido)napthoic acid; S,S′-disulfidobisacetic acid; S,S′-disulfidobisbenzoic acid; and S,S′-disulfidobisnapthoic acid.
[0620] S—O Valence Stabilizer #32: Examples of monothiomonocarboxylic acids, dithiodicarboxylic acids, bis(monothiomonocarboxylic acids), bis(dithiodicarboxylic acids), poly(monothiomonocarboxylic acids), poly(dithiodicarboxylic acids), and derivatives thereof (S—O Bidentates and S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: thioacetic acid; thiopropionic acid; thiobenzoic acid; thiophenylacetic acid; thiocyclohexanoic acid; thiofuroic acid; thionaphthoic acid; phenyl thioacetate; phenyl thiopropionate; phenyl thiobenzoate; phenyl thiocyclohexanoate; phenyl thiofuroate; phenyl thionaphthoate; dithiooxalic acid (dto); monothiooxalic acid (mtox); dithiomalonic acid; dithiosuccinic acid; diphenyl dithiooxalate; diphenyl dithiomalonate; and diphenyl dithiosuccinate.
[0621] S—O Valence Stabilizer #33: Examples of monothiocarbonates and bis(monothiocarbonates) (S—O Bidentates and S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: S,O-diethyldithiocarbonate; S,O-diisopropyldithiocarbonate; S,O-diphenyldithiocarbonate; S,O-dibenzyldithiocarbon ate; S,O-dicyclohexyldithiocarbonate; and S,O-dinorbornyldithiocarbonate.
[0622] S—O Valence Stabilizer #34: Examples of monothiocarbazates (monothiocarbazides), bis(monothiocarbazates), and poly(monothiocarbazates) (S—O Bidentates, S—O Tridentates, and S—O Tetradentates; or possibly N—S Bidentates, N—S Tridentates, and N—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: N,N′-dimethylmonothiocarbazate; N,N′-di(trifluoromethyl)monothiocarbazate; N,N′-diethylmonothiocarbazate; N,N′-diphenylmonothiocarbazate; N,N′-dibenzylmonothiocarbazate; N,N′-di(pentafluorophenyl)monothiocarbazate; N,N′-dicyclohexylmonothiocarbazate; and N,N′-dinorbornylmonothiocarbazate.
[0623] S—O Valence Stabilizer #35: Examples of mercapto alcohols and silylmercaptoalcohols, bis(mercapto alcohols and silylmercaptoalcohols), and poly(mercapto alcohols and silylmercaptoalcohols) (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-mercaptoethanol (mel); 3-mercaptopropanol (mpl); 2-mercaptophenol; 2-mercaptocyclohexanol; 3-mercapto-2-norborneol; 2-mercaptopyridine]-oxide; 1,4-thioxane; thiodialkanols; 2-(trimethoxysilyl)-1-ethanethiol (tmset); 3-(trimethoxysilyl)-1-propanethiol (tmspt); o-hydroxythiophenols; o-(O-hydroxyalkyl(aryl))thiophenols; and o-(S-thioalkyl(aryl))phenols.
[0624] S—O Valence Stabilizer #36: Examples of monothiocarbimates, bis(monothiocarbimates), and poly(monothiocarbimates) (S—O Bidentates, S—O Tridentates, and S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: methylmonothiocarbimate; trifluoromethylmonothiocarbimate; ethylmonothiocarbimate; propylmonothiocarbimate; isopropylmonothiocarbimate; butylmonothiocarbimate; tertbutylmonothiocarbimate; cyanomonothiocarbimate; cyanamidomonothiocarbimate; azidomonothiocarbimate; phenylmonothiocarbimate; pentafluorophenylmonothiocarbimate; benzylmonothiocarbimate; naphthylmonothiocarbimate; cyclohexylmonothiocarbimate; norbornylmonothiocarbimate; and adamantylmonothiocarbimate. [Note: Carbimates tend to stabilize lower oxidation states in metal ions.]
[0625] S—O Valence Stabilizer #37: Examples of alkyl- and aryl-monothioborates and bis(monothioborates) (S—O Bidentates and S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: O,O′-diethyl monothioborate; O,O′-diisopropyl monothioborate; O,O′-diphenyl monothioborate; O,O′-dibenzyl monothioborate; O,O′-dicyclohexyl monothioborate; and O,O′-dinorbornyl monothioborate.
[0626] S—O Valence Stabilizer #38: Examples of alkyl- and aryl-monothioboronates and bis(monothioboronates) (S—O Bidentates and S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diethyl monothioboronate; diisopropyl monothioboronate; diphenyl monothioboronate; dibenzyl monothioboronate; dicyclohexyl monothioboronate; and dinorbornyl monothioboronate. [Note: boronates tend to stabilize lower oxidation states in metal ions.]
[0627] S—O Valence Stabilizer #39: Examples of monothioarsonic acids (arsonothioic acids), bis(monothioarsonic acids), poly(monothioarsonic acids), and derivatives thereof (S—O Bidentates, S—O Tridentates, S—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: monothioarsonic acid, O-phenylmonothioarsonic acid, O-benzylmonothioarsonic acid, O-cyclohexylmonothioarsonic acid, O-norbornylmonothioarsonic acid, O,O-diphenylmonothioarsonic acid, O,O-dibenzylmonothioarsonic acid, O,O-dicyclohexylmonothioarsonic acid, and O,O-dinorbornylmonothioarsonic acid.
[0628] S—O Valence Stabilizer #40: Examples of heterocyclic rings containing one or two sulfur atoms and having at least one additional oxygen atom binding site not in a ring (S—O Bidentates, S—O Tridentates, S—O Tetradentates, or S—O Hexadentates) that meet the requirements for use as narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-thiopheneethanol (2-(2-thienyl)ethanol); 2-propionylthiophene (1-(2-thienyl)-1-propanone); N,N′-thiobisphthalimide; 1,1′-thiocarbonyldi-2-pyridone; 2-thiopheneacetic acid; 2-thiophenecarboxaldehyde; 2-thiophenecarboxamide; 2-thiophenecarboxylic acid; 2,5-thiophenedicarboxaldehyde; 2,5-thiophenedicarboxylic acid; 2-thiophenemethanol; 2-thiophenone; thiotetronic acid; alkyl(aryl) 2-thienyl ketones; dithienyl ketone; 1,3-dithiane-2-carboxylic acid; and 1,3-dithiolane-2-carboxylic acid.
[0629] S—O Valence Stabilizer #41: Examples of heterocyclic rings containing one or two oxygen atoms and having at least one-additional sulfur atom binding site not in a ring (S—O Bidentates, S—O Tridentates, S—O Tetradentates, or S—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-furanethanethiol (2-(2-furyl)thanethiol); 1-(2-furyl)-1-propanethione); 2-furanthioacetic acid; 2-furanthiocarboxaldehyde; 2-furanthiocarboxamide; 2-furanthiocarboxylic acid; 2,5-furandithiocarboxaldehyde; 2,5-furandithiocarboxylic acid; 2-furanmethanethiol; 2-furanthione; furfuryl disulfide; furfuryl mercaptan; furfuryl sulfide; and furfuryl methyl disulfide.
[0630] S—O Valence Stabilizer #42: Examples of heterocyclic rings containing one or two sulfur atoms and having at least one additional oxygen atom binding site in a separate ring (S—O Bidentates, S—O Tridentates, S—O Tetradentates, or S—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-(2-furyl)thiophene; 2,5-(2-furyl)thiophene; 2-(2-furyl)thiopyran; and 2,5-(2-furyl)thiopyran.
[0631] S—O Valence Stabilizer #43: Examples of two-, three-, four-, five-, six-, seven-, eight-, nine-, and ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of sulfur (usually thiol, mercapto, or thiocarbonyl groups) or oxygen (hydroxy, carboxy, or carbonyl groups) and are not contained in component heterocyclic rings (S—O Bidentates, S—O Tridentates, S—O Tetradentates, and S—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: thiaoxacyclobutane ([4]aneOS); thiaoxacyclopentane ([5]aneOS); thiaoxacyclohexane ([6]aneOS); thiaoxacycloheptane ([7]aneOS); thiaoxacyclooctane ([8]aneOS); thiaoxacyclobutene ([4]eneOS); thiaoxacyclopentene ([5]eneOS); thiaoxacyclohexene ([6]eneOS); thiaoxacycloheptene ([7]eneOS); thiaoxacyclooctene ([8]eneOS); dithiaoxacyclohexane ([6]aneOS2); dithiaoxacycloheptane ([7]aneOS2); dithiaoxacyclooctane ([8]aneOS2); dithiaoxacyclononane ([9]aneOS2); dithiaoxacyclodecane ([10]aneOS2); dithiaoxacycloundecane ([1]aneOS2); dithiaoxacyclododecane ([12]aneOS2); dithiaoxacyclohexene ([6]eneOS2); dithiaoxacycloheptene ([7]eneOS2); dithiaoxacyclooctene ([8]encOS2); dithiaoxacyclononene ([9]eneOS2); dithiaoxacyclodecene ([10]eneOS2); dithiaoxacycloundecene ([11]eneOS2); dithiaoxacyclododecene ([12]eneOS2); dithiadioxacyclooctane ([8]aneO2S2); dithiadioxacyclononane ([9]aneO2S2); dithiadioxacyclodecane ([10]aneO2S2); dithiadioxacycloundecane ([11]aneO2S2); dithiadioxacyclododecane ([12]aneO2S2); dithiadioxacyclotridecane ([13]aneO2S2); dithiadioxacyclotetradecane ([14]aneO2S2); dithiadioxacyclopentadecane ([15]aneO2S2); dithiadioxacyclohexadecane ([16]aneO2S2); dithiadioxacycloheptadecane ([17]aneO2S2); dithiadioxacyclooctadecane ([18]aneO2S2); dithiadioxacyclononadecane ([19]aneO2S2); dithiadioxacycloeicosane ([20]aneO2S2); dithiadioxacyclooctadiene ([8]dieneO2S2); dithiadioxacyclononadiene ([9]dieneO2S2); dithiadioxacyclodecadiene ([10]dieneO2S2); dithiadioxacycloundecadiene ([11]dieneO2S2); dithiadioxacyclododecadiene ([12]dieneO2S2); dithiadioxacyclotridecadiene ([13]dieneO2S2); dithiadioxacyclotetradecadiene ([14]dieneO2S2); dithiadioxacyclopentadecadiene ([15]dieneO2S2); dithiadioxacyclohexadecadiene ([16]dieneO2S2); dithiadioxacycloheptadecadiene ([17]dieneO2S2); dithiadioxacyclooctadecadiene ([18]dieneO2S2); dithiadioxacyclononadecadiene ([19]dieneO2S2); and dithiadioxacycloeicosadiene ([20]dieneO2S2).
[0632] S—O Valence Stabilizer #44: Examples of four-, five-, six-, seven-, eight-, nine-, or ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of sulfur or oxygen and are contained in component heterocyclic rings (S—O Tridentates, S—O Tetradentates, or S—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: difurandithiophenes; difurantrithiophenes; trifurantritbiophenes; and tetrafurantetratbiophenes.
[0633] S—O Valence Stabilizer #45: Examples of four-, five-, six-, seven-, eight-, nine-, or ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of sulfur or oxygen and are contained in a combination of heterocyclic rings and thiol, mercapto, thiocarbonyl, hydroxy, carboxy, and carbonyl groups (S—O Tridentates, S—O Tetradentates, or S—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dithiadifurandithiophenes; tetrathiadifurandithiophenes; trithiatrifurantrithiophenes; trithiatrifurantrithiophenes; tetrathiatetrafurantetrathiophenes; and octathiatetrafurantetrathiophenes.
[0634] S—O Valence Stabilizer #46: Examples of sulfoxides that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dimethylsulfoxide (DMSO); diethylsulfoxide; diphenylsulfoxide; and tetrahydrothiophene oxide.
[0635] S—O Valence Stabilizer #47: Examples of sulfones that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dimethyl sulfone; diethyl sulfone; and diphenyl sulfone.
[0636] S—O Valence Stabilizer #48: Examples of sulfur dioxide ligands that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: sulfur dioxide (—SO2) ligands. [Note: Sulfur dioxide is a reducing agent, and complexed metal ions therefore tend to prefer lower oxidation states.]
[0637] N—P Valence Stabilizer #1: Examples of aminoaryl phosphines and iminoaryl phosphines (N—P Bidentates, N—P Tridentates, and N—P Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: tri(2-aminophenyl)phosphine; tri(2-aminophenyl)phosphine oxide; and tri(2-aminopbenyl)phosphine sulfide.
[0638] N—P Valence Stabilizer #2: Examples of heterocyclic rings containing one, two, three, or four nitrogen atoms and having at least one additional phosphorus atom binding site not in a ring (N—P Bidentates, N—P Tridentates, N—P Tetradentates, or N—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: tri(2-imidazolyl)phosphine; tri(2-pyrrolyl)phosphine; tri(2-pyridyl)phosphine; tri(2-imidazolyl)phosphine oxide; tri(2-pyrrolyl)phosphine oxide; tri(2-pyridyl)phosphine oxide; tri(2-imidazolyl)phosphine sulfide; tri(2-pyrrolyl)phosphine sulfide; and tri(2-pyridyl)phosphine sulfide.
[0639] N—P Valence Stabilizer #3: Examples of heterocyclic rings containing one, two, or three phosphorus atoms and having at least one additional nitrogen atom binding site not in a ring (N—P Bidentates, N—P Tridentates, N—P Tetradentates, or N—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-aminophosphole; 2,5-diaminophosphole; 2-(aminomethyl)phosphole; 2,5-di(aminomethyl)phosphole; 2-aminophosphorin; 2,6-diaminophosphorin; 2-(aminomethyl)phosphorin; 2,6-di(aminomethyl)phosphorin; triaminocyclotriphosphazenes; and hexaminocyclotriphosphazenes.
[0640] N—P Valence Stabilizer #4: Examples of heterocyclic rings containing one, two, three, or four nitrogen atoms and having at least one additional phosphorus atom binding site in a separate ring (N—P Bidentates, N—P Tridentates, N—P Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-(2-pyrrolyl)phosphole; 2,5-di(2-pyrrolyl)phosphole; 2-(2-pyridyl)phosphorin; and 2,6-(2-pyridyl)phosphorin.
[0641] N—P Valence Stabilizer #5: Examples of two-, three-, four-, five-, six-, seven-, eight-, nine-, and ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen (usually amine or imine groups) or phosphorus and are not contained in component heterocyclic rings (N—P Bidentates, N—P Tridentates, N—P Tetradentates, and N—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: cyclobiphosphazenes; cyclotriphosphazenes; cyclotetraphosphazenes; cyclopentaphosphazenes; cyclohexaphosphazenes; diphosphatetraazacyclooctatetraenes; diphospha-s-triazines; and phospha-s-triazines.
[0642] N—P Valence Stabilizer #6: Examples of four-, five-, six-, seven-, eight-, nine-, or ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen or phosphorus and are contained in component heterocyclic rings (N—P Bidentates, N—P Tridentates, N—P Tetradentates, or N—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diphospholedipyrroles; diphosphorindipyridines; triphospholetripyrroles; triphosphorintripyridines; tetraphospholetetrapyrroles; and tetraphosphorintetrapyridines.
[0643] N—P V alence Stabilizer #7: Examples of four-, five-, six-, seven-, eight-, nine-, or ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of nitrogen or phosphorus and are contained in a combination of heterocyclic rings and amine, imine, and phosphine groups (N—P Bidentates, N—P Tridentates, N—P Tetradentates, or N—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: azaphosphatetraphyrins; diazadiphosphatetraphyrins; azaphosphahexaphyrins; diazadiphosphahexaphyrins; triazatriphosphahexaphyrins; and apholate.
[0644] S—P Valence Stabilizer #1: Examples of thioaryl phosphines (S—P Bidentates, S—P Tridentates, S—P Tetradentates, and S—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: tri(2-mercaptophenyl)phosphine; tri(2-mercaptophenyl)phosphine oxide; and tri(2-inercaptophenyl)phosphine sulfide.
[0645] S—P Valence Stabilizer #2: Examples of heterocyclic rings containing one or two sulfur atoms and having at least one additional phosphorus atom binding site not in a ring (S—P Bidentates, S—P Tridentates, S—P Tetradentates, or S—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: tri(2-thiophene)phosphine; tri(2-thiopyran)phosphine; tri(2-thiophene)phosphine oxide; tri(2-thiopyran)phosphine oxide; tri(2-thiophene)phosphine sulfide; and tri(2-thiopyran)phosphine sulfide.
[0646] S—P Valence Stabilizer #3: Examples of heterocyclic rings containing one, two, or three phosphorus atoms and having at least one additional sulfur atom binding site not in a ring (S—P Bidentates, S—P Tridentates, S—P Tetradentates, or S—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-mercaptophosphole; 2,5-dimercaptophosphole; 2-(mercaptomethyl)phosphole; 2,5-di(mercaptomethyl)phosphole; 2-mercaptophosphorin; 2,6-dimercaptophosphorin; 2-(mercaptomethyl)phosphorin; and 2,6-di(mercaptomethyl)phosphorin.
[0647] S—P Valence Stabilizer #4: Examples of heterocyclic rings containing one or two sulfur atoms and having at least one additional phosphorus atom binding site in a separate ring (S—P Bidentates, S—P Tridentates, S—P Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-(2-thienyl)phosphole; 2,5-di(2-thienyl)phosphole; 2-(2-thienyl)phosphorin; and 2,6-(2-thienyl)phosphorin.
[0648] S—P Valence Stabilizer #5: Examples of two-, three-, four-, five-, six-, seven-, eight-, nine-, and ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of sulfur (usually thiol, mercapto, or thiocarbonyl groups) or phosphorus and are not contained in component heterocyclic rings (S—P Bidentates, S—P Tridentates, S—P Tetradentates, and S—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: phosphathiacyclobutane ([4]anePS); phosphathiacyclopentane ([5]anePS); phosphathiacyclohexane ([6]anePS); phosphathiacycloheptane ([7]anePS); phosphathiacyclooctane ([8]anePS); diphospbathiacyclohexane ([6]aneSP2); diphosphathiacycloheptane ([7]aneSP2); diphosphathiacyclooctane ([8]aneSP2); diphosphathiacyclononane ([9]aneSP2); diphosphathiacyclodecane ([10]aneSP2); diphosphathiacycloundecane ([11]aneSP2); diphosphathiacyclododecane ([12]aneSP2); diphosphadithiacyclooctane ([8]aneS2P2); diphosphadithiacyclononane ([9]aneS2P2); diphosphadithiacyclodecane ([10] aneS2P2); diphospbadithiacycloundecane ([11]aneS2P2); diphosphadithiacyclododecane ([12]aneS2P2); diphosphadithiacyclotridecane ([13]aneS2P2); diphosphadithiacyclotetradecane ([14]aneS2P2); diphosphadithiacyclopentadecane ([15]aneS2P2); diphosphadithiacyclohexadecane ([16]aneS2P2); diphosphadithiacycloheptadecane ([17]aneS2P2); diphosphadithiacyclooctadecane ([18]aneS2P2); diphosphadithiacyclononadecane ([19]aneS2P2); diphosphadithiacycloeicosane ([20]aneS2P2).
[0649] S—P Valence Stabilizer #6: Examples of four-, five-, six-, seven-, eight-, nine-, or ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of sulfur or phosphorus and are contained in component heterocyclic rings (S—P Bidentates, S—P Tridentates, S—P Tetradentates, or S—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diphospholedithiophenes; diphosphorindithiopyrans; triphospholetrithiophenes; triphosphorintrithiopyrans; tetraphospholetetrathiophenes; and tetraphosphorintetrathiopyrans.
[0650] S—P Valence Stabilizer #7: Examples of four-, five-, six-, seven-, eight-, nine-, or ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of sulfur or phosphorus and are contained in a combination of heterocyclic rings and thiol, mercapto, thiocarbonyl, and phosphine groups (S—P Bidentates, S—P Tridentates, S—P Tetradentates, or S—P Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: thiaphosphatetraphyrins; dithiadiphosphatetraphyrins; thiaphosphahexaphyrins; dithiadiphosphahexaphyrins; and trithiatriphosphahexaphyrins.
[0651] P—O Valence Stabilizer #1: Examples of hydroxyaryl phosphines (P—O Bidentates, P—O Tridentates, P—O Tetradentates, and P—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: tri(2-hydroxyphenyl)phosphine; tri(2-hydroxyphenyl)phosphine oxide; and tri(2-hydroxyphenyl)phosphine sulfide.
[0652] P—O Valence Stabilizer #2: Examples of heterocyclic rings containing one or two oxygen atoms and having at least one additional phosphorus atom binding site not in a ring (P—O Bidentates, P—O Tridentates, P—O Tetradentates, or P—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: tri(2-furan)phosphine; tri(2-pyran)phosphine; tri(2-furan)phosphine oxide; tri(2-pyran)phosphine oxide; tri(2-furan)phosphine sulfide; and tri(2-pyran)phosphine sulfide.
[0653] P—O Valence Stabilizer #3: Examples of heterocyclic rings containing one, two, or three phosphorus atoms and having at least one additional oxygen atom binding site not in a ring (P—O Bidentates, P—O Tridentates, P—O Tetradentates, or P—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-hydroxyphosphole; 2,5-dihydroxyphosphole; 2-(hydroxymethyl)phosphole; 2,5-di(hydroxymethyl)phosphole; 2-hydroxyphosphorin; 2,6-dihydroxyphosphorin; 2-(hydroxymethyl)phosphorin; and 2,6-di(hydroxymethyl)phosphorin.
[0654] P—O Valence Stabilizer #4: Examples of heterocyclic rings containing one or two oxygen atoms and having at least one additional phosphorus atom binding site in a separate ring (P—O Bidentates, P—O Tridentates, P—O Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-(2-furyl)phosphole; 2,5-di(2-furyl)phosphole; 2-(2-furyl)phosphorin; and 2,6-(2-furyl)phosphorin.
[0655] P—O Valence Stabilizer #5: Examples of two-, three-, four-, five-, six-, seven-, eight-, nine-, and ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of oxygen (usually hydroxy, carboxy, or carbonyl groups) or phosphorus and are not contained in component heterocyclic rings (P—O Bidentates, P—O Tridentates, P—O Tetradentates, and P—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: phosphaoxacyclobutane ([4]anePO); phosphaoxacyclopentane ([5]anePO); phosphaoxacyclohexane ([6]anePO); phosphaoxacycloheptane ([7]anePO); phosphaoxacyclooctane ([8]anePO); diphosphaoxacyclohexane ([6]aneOP2); diphosphaoxacycloheptane ([7]aneOP2); diphosphaoxacyclooctane ([8]aneOP2); diphosphaoxacyclononane ([9]aneOP2); diphosphaoxacyclodecane ([10]aneOP2); diphosphaoxacycloundecane ([11]aneOP2); diphosphaoxacyclododecane ([12]aneOP2); diphosphadioxacyclooctane ([8]aneO2P2); diphosphadioxacyclononane ([9]aneO2P2); diphosphadioxacyclodecane ([10]aneO2P2); diphosphadioxacycloundecane ([1]aneO2P2); diphosphadioxacyclododecane ([12]aneO2P2); diphosphadioxacyclotridecane ([13]aneO2P2); diphosphadioxacyclotetradecane ([14]aneO2P2); diphosphadioxacyclopentadecane ([15]aneO2P2); diphosphadioxacyclohexadecane ([16]aneO2P2); diphosphadioxacycloheptadecane ([17]aneO2P2); diphosphadioxacyclooctadecane ([18]aneO2P2); diphosphadioxacyclononadecane ([19]aneO2P2); diphosphadioxacycloeicosane ([20]aneO2P2); and dioxaphospholane.
[0656] P—O Valence Stabilizer #6: Examples of four-, five-, six-, seven-, eight-, nine-, or ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of oxygen or phosphorus and are contained in component heterocyclic rings (P—O Bidentates, P—O Tridentates, P—O Tetradentates, or P—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diphospholedifurans; diphosphorindipyrans; triphospholetrifurans; triphosphorintripyrans; tetraphospholetetrafurans; and tetraphosphorintetrapyrans.
[0657] P—O Valence Stabilizer #7: Examples of four-, five-, six-, seven-, eight-, nine-, or ten-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of oxygen or phosphorus and are contained in a combination of heterocyclic rings and hydroxy, carboxy, caibonyl, and phosphine groups (P—O Bidentates, P—O Tridentates, P—O Tetradentates, or P—O Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: oxaphosphatetraphyrins; dioxadiphosphatetraphyrins; oxaphosphahexaphyrins; dioxadiphosphahexaphyrins; and trioxatriphosphahexaphyrins.
[0658] As Valence Stabilizer #1: Examples of monoarsines (As Monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: arsine, triphenylarsine, ticyclohexylarsine, methyldiphenylarsine, ethyldiphenylarsine, arsinonorbornane, and arsinoadamantane.
[0659] As Valence Stabilizer #2: Examples of diarsines (As Monodentates or As—As Bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: bis(diphenylarsino)methane, bis(diphenylarsino)ethane, bis(diphenylarsino)propane, bis(diphenylarsino)butane, bis(diphenylarsino)pentane, 1,2-diarsinobenzene, cyclohexane-1,2-diarsine, 1,2-bis(phenylbutylarsino)ethane, o-phenylenebis(methylphenylarsine) and o-phenylenebis(dimethylarsine) (diars). (Note: the aryl derivatives are air-stable, whereas the alkyl derivatives are air-sensitive and therefore unsuitable for these applications.)
[0660] As Valence Stabilizer #3: Examples of triarsines (As—As Bidentates, or As—As Tridentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 1,1,5,9,9-pentaphenyl-1,5,9-triarsanonane, 3-methyl-3-(As,As-dimethyl)arsinomethyl-1,1,5,5-tetraphenyl-1,5-diarsapentane, As,As-[o-(As-dimethyl)arsinodiphenyl]-(As-phenyl)arsine, As,As-[o-(As-diphenyl)arsinodiphenyl]-(As-phenyl)arsine, hexahydro-2,4,6-trimethyl-1,3,5-triarsinazine. (Note: the aryl derivatives are air-stable, whereas the alkyl derivatives are air-sensitive and therefore unsuitable for these applications.)
[0661] As Valence Stabilizer #4: Examples of tetraarsines (As—As Bidentates, As—As Tridentates, or As—As Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 3,3-(As-diphenyl)arsinomethyl-1,1,5,5-tetraphenyl-1,5-diarsapentane. (Note: the aryl derivatives are air-stable, whereas the alkyl derivatives are air-sensitive and therefore unsuitable for these applications.)
[0662] As Valence Stabilizer #5: Examples of pentaarsines (As—As Bidentates, As—As Tridentates, or As—As Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 4-[2-(As-diphenyl)arsinoethyl]-1,1,7,10,10-pentaphenyl-1,4,7,10-tetraarsadecane. (Note: the aryl derivatives are air-stable, whereas the alkyl derivatives are air-sensitive and therefore unsuitable for these applications.)
[0663] As Valence Stabilizer #6: Examples of hexaarsines (As—As Bidentates, As—As Tridentates, As—As Tetradentates, or As—As Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: o-phenylenebis[di-3-(As-diphenyl)arsinopropylarsine]. (Note: the aryl derivatives are air-stable, whereas the alkyl derivatives are air-sensitive and therefore unsuitable for these applications.)
[0664] As Valence Stabilizer #7: Examples of 5-membered heterocyclic rings containing one arsenic atom (As Monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: arsole, azarsole, diazarsole, benzarsole, benzazarsole, dibenzarsole, naphtharsole, naphthazarsole.
[0665] As Valence Stabilizer #8: Examples of 6-membered heterocyclic rings containing one arsenic atom (As Monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: arsenin, azarsenin, diazarsenin, benzarsenin, benzazarsenin, dibenzarsenin, naphtharsenin, and naphthazarsenin.
[0666] As Valence Stabilizer #9: Examples of 5-membered heterocyclic rings containing one arsenic atom and having at least one additional arsenic atom binding site not contained in a ring (As Monodentates, As—As Bidentates, As—As Tridentates, As—As Tetradentates, or As—As Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-(As-phenylarsino)arsole; 2,5-(As-phenylarsino)arsole; 2-(As-phenylarsino)benzarsole; 7-(As-phenylarsino)benzarsole; and 1,8-(As-phenylarsino)dibenzarsole.
[0667] As Valence Stabilizer #10: Examples of 6-membered heterocyclic rings containing one arsenic atom and having at least one additional arsenic atom binding site not contained in a ring (As Monodentates, As—As Bidentates, As—As Tridentates, As—As Tetradentates, or As—As Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2-(As-phenylarsino)arsenin; 2,5-(As-phenylarsino)arsenin; 2-(As-phenylarsino)benzarsenin; 7-(As-phenylarsino)benzarsenin; and 1,9-(As-phenylarsino)dibenzarsenin.
[0668] As Valence Stabilizer #11: Examples of 5-membered heterocyclic rings containing one arsenic atom and having at least one additional arsenic atom binding site contained in a ring (As Monodentates, As—As Bidentates, As—As Tridentates, As—As Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2,2′-biarsole; 2,2′,2″-triarsole; and 2,2′-bibenzarsole.
[0669] As Valence Stabilizer #12: Examples of 6-membered heterocyclic rings containing one arsenic atom and having at least one additional arsenic atom binding site contained in a ring (As Monodentates, As—As Bidentates, As—As Tridentates, As—As Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2,2′-biarsenin; 2,2′,2″-triarsenin; 2,2′,2″,2′″-tetraarsenin; 2,2′-bibenzarsenin; and 8,8′-bibenzarsenin.
[0670] As Valence Stabilizer #13a: Examples of two-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein both binding sites are composed of arsenic and are not contained in component heterocyclic rings (As—As Bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: As,As-diphenyldiarsacyclobutane ([4]aneAs2); As,As-diphenyldiarsacyclopentane ([5]aneAs2); As,As-diphenyldiarsacyclohexane ([6]aneAs2); As,As-diphenyldiarsacycloheptane ([7]aneAs2); As,As-diphenyldiarsacyclooctane ([8]aneAs2); As,As-diphenyldiarsacyclobutene ([4]eneAs2); As,As-diphenyldiarsacyclopentene ([5]eneAs2); As,As-diphenyldiarsacyclohexene ([6]eneAs2); As,As-diphenyldiarsacycloheptene ([7]eneAs2); and As,As-diphenyldiarsacyclooctene ([8]eneAs2).
[0671] As Valence Stabilizer #13b: Examples of three-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of arsenic and are not contained in component heterocyclic rings (As—As Tridentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: As,As,As-triphenyltriarsacyclohexane ([6]aneAs3); As,As,As-triphenyltriarsacycloheptane ([7]aneAs3); As,As,As-triphenyltriarsacyclooctane ([8]aneAs3); As,As,As-triphenyltriarsacyclononane ([9]aneAs3); As,As,As-triphenyltriarsacyclodecane ([10]aneAs3); As,As,As-triphenyltriarsacycloundecane ([11]aneAs3); As,As,As-triphenyltriarsacyclododecane ([12]aneAs3); As,As,As-triphenyltriarsacyclohexatriene ([6]trieneAs3); As,As,As-triphenyltriarsacycloheptatriene ([7]trieneAs3); As,As,As-triphenyltriarsacyclooctatriene ([8]trieneAs3); As,As,As-triphenyltriarsacyclononatriene ([9]trieneAs3); As,As,As-triphenyltriarsacyclodecatriene ([10]trieneAs3); As,As,As-triphenyltriarsacycloundecatriene ([11]trieneAs3); and As,As,As-triphenyltriarsacyclododecatriene ([12]trieneAs3).
[0672] As Valence Stabilizer #13c: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of arsenic and are not contained in component heterocyclic rings (As—As Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: As,As,As,As-tetraphenyltetraarsacyclooctane ([8]aneAs4); As,As,As,As-tetraphenyltetraarsacyclononane ([9]aneAs4); As,As,As,As-tetraphenyltetraarsacyclodecane ([10]aneAs4); As,As,As,As-tetraphenyltetraarsacycloundecane ([11]aneAs4); As,As,As,As-tetraphenyltetraarsacyclododecane ([12]aneAs4); As,As,As,As-tetraphenyltetraarsacyclotridecane ([13]aneAs4); As,As,As,As-tetraphenyltetraarsacyclotetradecane ([14]aneAs4); As,As,As,As-tetraphenyltetraarsacyclopentadecane ([15]aneAs4); As,As,As,As-tetraphenyltetraarsacyclohexadecane ([16]aneAs4); As,As,As,As,As-etraphenyltetraarsacycloheptadecane ([17]aneAs4); As,As,As,As-etraphenyltetraarsacyclooctadecane ([18]aneAs4); As,As,As,As-etraphenyltetraarsacyclononadecane ([19]aneAs4); and As,As,As,As-tetraphenyltetraarsacycloeicosane ([20]aneAs4).
[0673] As Valence Stabilizer #13d: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of arsenic and are not contained in component heterocyclic rings (As—As Tridentates, As—As Tetradentates, or As—As Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: As,As,As,As,As,As-hexaphenylhexaarsacyclododecane ([12]aneAs6); As—As,As,As,As,As-hexaphenylhexaarsacyclotridecane ([13]aneAs6); As,As,As,As,As,As-hexaphenylhexaarsacyclotetradecane ([14]aneAs6); As,As,As,As,As,As-hexaphenylhexaarsacyclopentadecane ([15]aneAs6); As,As,As,As,As,As-hexaphenylhexaarsacyclohexadecane ([16]aneAs6); As,As,As,As,As,As-hexaphenylhexaarsacycloheptadecane ([17]aneAs6); As,As,As,As,As,As-hexaphenylhexaarsacyclooctadecane ([18]aneAs6); As,As,As,As,As,As-hexaphenylhexaarsacyclononadecane ([19]aneAs6); As,As,As,As,As,As-hexaphenylhexaarsacycloeicosane ([20]aneAs6); As,As,As,As,As,As-hexaphenylhexaarsacycloheneicosane ([21]aneAs6); As,As,As,As,As,As-hexaphenylhexaarsacyclodocosane ([22]aneAs6); As,As,As,As,As,As-hexaphenylhexaarsacyclotricosane ([23]aneAs6); and As,As,As,As,As,As-hexaphenylhexaarsacyclotetracosane ([24]aneAs6).
[0674] As Valence Stabilizer #14a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of arsenic and are contained in component 5-membered heterocyclic rings (As—As Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: tetraarsoles.
[0675] As Valence Stabilizer #14b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of arsenic and are contained in component 5-membered heterocyclic rings (As—As Tetradentates and As—As Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: hexaarsoles.
[0676] As Valence Stabilizer #15a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of arsenic and are contained in a combination of 5-membered heterocyclic rings and arsine groups (As—As Tridentates, As—As Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diarsatetraarsoles; and tetraarsatetraarsoles.
[0677] As Valence Stabilizer #15b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of arsenic and are contained in a combination of 5-membered heterocyclic rings and phosphine groups (As—As Tridentates, As—As Tetradentates, and As—As Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diarsahexaarsoles; and triarsahexaarsoles.
[0678] As Valence Stabilizer #16a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of arsenic and are contained in component 6-membered heterocyclic rings (As—As Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: cyclotetraarsenins.
[0679] As Valence Stabilizer #16b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of arsenic and are contained in component 6-membered heterocyclic rings (As—As Tridentates, As—As Tetradentates, and As—As Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: cyclohexaarsenins.
[0680] As Valence Stabilizer #17a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of arsenic and are contained in a combination of 6-membered heterocyclic rings and arsine groups (As—As Tridentates, As—As Tetradentates, or As—As Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diarsacyclotetraarsenins; and tetraarsacyclotetraarsenins.
[0681] As Valence Stabilizer #17b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of arsenic and are contained in a combination of 6-membered heterocyclic rings and arsine groups (As—As Tridentates, As—As Tetradentates, or As—As Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diarsacyclohexaarsenins; and triarsacyclohexaarsenins.
[0682] Se Valence Stabilizer #1: Examples of monoselenoethers (Se Monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: hydrogen selenide, dimethyl selenide, diethyl selenide, dioctyl selenide, diphenyl selenide, dicyclohexyl selenide, tetramethylene selenide, trimethylene selenide, dimethylene selenide, and selenobicycloheptane.
[0683] Se Valence Stabilizer #2: Examples of diselenoethers (Se Bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2,5-dimethyl-3,6-diselenaoctane; 2,5-diselenahexane; 2,6-diselenaheptane; 3,7-diselenanonane; 3,6-diselenaoctane; 3-butenyl butyl selenoether (bbs); 4-pentenyl butyl selenoether (pbs); 3-butenyl phenyl selenoether (bps); and 4-pentenyl phenyl selenoether (pps).
[0684] Se Valence Stabilizer #3: Examples of triselenoethers (Se Bidentates or Se Tridentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 1,3,5-triselenane; 2,5,8-triselenanonane; 3,6,9-triselenaundecane; and 2,6,10-triselenaundecane.
[0685] Se Valence Stabilizer #4: Examples of tetraselenoethers (Se Bidentates, Se Tridentates, or Se Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2,6,10,14-tetraselenapentadecane and 2,5,8,11-tetraselenadodecane.
[0686] Se Valence Stabilizer #5a: Examples of 5-membered heterocyclic rings containing one selenium atom (Se Monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dihydroselenophene, selenophene, selenazole, selenapyrroline, selenaphospholene, selenaphosphole, oxaselenole, selenadiazole, selenatriazole, benzodihydroselenophene, benzoselenophene, benzoselenazole, benzoselenaphosphole, dibenzoselenophene, and naphthoselenophene.
[0687] Se Valence Stabilizer #5b: Examples of 5-membered heterocyclic rings containing two selenium atoms (Se Monodentates or Se Bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diselenole, benzodiselenole, and naphthodiselenole.
[0688] Se Valence Stabilizer #6a: Examples of 6-membered heterocyclic rings containing one selenium atom (Se Monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dihydroselenopyran, selenopyran, selenazine, selenadiazine, selenaphosphorin, selenadiphosphorin, oxaselenin, benzoselenopyran, dibenzoselenopyran, and naphthoselenopyran.
[0689] Se Valence Stabilizer #6b: Examples of 6-membered heterocyclic rings containing two selenium atoms (Se Monodentates or Se Bidentates)that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dihydrodiselenin, diselenin, benzodiselenin, dibenzodiselenin, and naphthodiselenin.
[0690] Se Valence Stabilizer #7: Examples of 5-membered heterocyclic rings containing one selenium atom and having at least one additional selenium atom binding site not contained in a ring (Se Monodentates, Se—Se Bidentates, Se—Se Tridentates, Se—Se Tetradentates, or Se—Se Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2,5-diseleno-2,5-dihydroselenophene; 2,5-bis(selenomethyl)-2,5-dihydroselenophene; 2,5-bis(2-selenophenyl)-2,5-dihydroselenophene; 2,5-diseleno(selenophene); 2,5-bis(selenomethyl)selenophene; 2,5-bis(2-selenophenyl)selenophene; 2,5-diseleno(selenazole); 2,5-bis(selenomethyl)selenazole; 2,5-bis(2-selenophenyl)selenazole; and 2,5-diseleno-1,3,4-selenadiazole [bismuthselenol].
[0691] Se Valence Stabilizer #8: Examples of 6-membered heterocyclic rings containing one selenium atom and having at least one additional selenium atom binding site not contained in a ring (Se Monodentates, Se—Se Bidentates, Se—Se Tridentates, Se—Se Tetradentates, or Se—Se Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2,6-diseleno-2,5-dihydroselenopyran; 2,6-bis(selenomethyl)-2,5-dihydroselenopyran; 2,6-bis(2-selenophenyl)-2,5-dihydroselenopyran; 2,6-diseleno(selenopyran); 2,6-bis(selenomethyl)selenopyran; 2,6-bis(2-selenophenyl)selenopyran; 2,6-diseleno(selenazine); 2,6-bis(selenomethyl)selenazine; 2,6-bis(2-selenophenyl)selenazine; 2,6-diseleno-1,3,5-selenadiazine; 2-seleno-1-benzoselenopyran; 8-seleno-1-benzoselenopyran; and 1,9-diselenodibenzoselenopyran.
[0692] Se Valence Stabilizer #9: Examples of 5-membered heterocyclic rings containing one selenium atom and having at least one additional selenium atom binding site contained in a ring (Se Monodentates, Se—Se Bidentates, Se—Se Tridentates, Se—Se Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2,2′-bi-2,5-dihydroselenophene; 2,2′,2″-tri-2,5-dihydroselenophene; 2,2′-biselenophene; 2,2′,2″-triselenophene; 2,2′-biselenazole; 5,5′-biselenazole; 2,2′-bi-1,3,4-selenadiazole; 2,2′-biselenanaphthene; 2,2′-bibenzoselenazole; and 1,1′-bis(dibenzoselenophene).
[0693] Se Valence Stabilizer #10: Examples of 6-membered heterocyclic rings containing one selenium atom and having at least one additional selenium atom binding site contained in a ring (Se Monodentates, Se—Se Bidentates, Se—Se Tridentates, Se—Se Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 2,2′-bi-2,5-dihydroselenopyran; 2,2′,2″-tri-2,5-dihydroselenopyran; 2,2′-biselenopyran; 2,2′,2″-triselenopyran; 2,2′-bi-1,4-selenazine; 2,2′-bi-1,3,5-selenadiazine; 2,2′-bi-1-benzoselenopyran; and 1,1′-bis(dibenzoselenopyran).
[0694] Se Valence Stabilizer #11a: Examples of two-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein both binding sites are composed of selenium (usually selenol or selenoether groups) and are not contained in component heterocyclic rings (Se—Se Bidentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diselenacyclobutane ([4]aneSe2); diselenacyclopentane ([5]aneSe2); diselenacyclohexane ([6]aneSe2); diselenacycloheptane ([7]aneSe2); diselenacyclooctane ([8]aneSe2); diselenacyclobutene ([4]eneSe2); diselenacyclopentene ([5]eneSe2); diselenacyclohexene ([6]eneSe2); diselenacycloheptene ([7]eneSe2); diselenacyclooctene ([8]eneSe2); diselenacyclobutadiene ([4]dieneSe2); diselenacyclopentadiene ([5]dieneSe2); diselenacyclohexadiene ([6]dieneSe2); diselenacycloheptadiene ([7]dieneSe2); and diselenacyclooctadiene ([8]dieneSe2).
[0695] Se Valence Stabilizer #11b: Examples of three-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of selenium (usually selenol or selenoether groups) and are not contained in component heterocyclic rings (Se—Se Tridentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: triselenacyclohexane ([6]aneSe3); triselenacycloheptane ([7]aneSe3); triselenacyclooctane ([8]aneSe3); triselenacyclononane ([9]aneSe3); triselenacyclodecane ([10]aneSe3); triselenacycloundecane ([11]aneSe3); triselenacyclododecane ([12]aneSe3); triselenacyclohexene ([6]eneSe3); triselenacycloheptene ([7]eneSe3); triselenacyclooctene ([8]eneSe3); triselenacyclononene ([9]eneSe3); triselenacyclodecene ([10]eneSe3); triselenacycloundecene ([11]eneSe3); triselenacyclododecene ([12]eneSe3); triselenacyclohexatriene ([6]trieneSe3); triselenacycloheptatriene ([7]trieneSe3); triselenacyclooctatriene ([8]trieneSe3); triselenacyclononatriene ([9]trieneSe3); triselenacyclodecatriene ([10]trieneSe3); triselenacycloundecatriene ([11]trieneSe3); and triselenacyclododecatriene ([12]trieneSe3).
[0696] Se Valence Stabilizer #11c: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of selenium (usually selenol or selenoether groups) and are not contained in component heterocyclic rings (Se—Se Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: tetraselenacyclooctane ([8]aneSe4); tetraselenacyclononane ([9]aneSe4); tetraselenacyclodecane ([10]aneSe4); tetraselenacycloundecane ([11]aneSe4); tetraselenacyclododecane ([12]aneSe4); tetraselenacyclotridecane ([13]aneSe4); tetraselenacyclotetradecane ([14]aneSe4); tetraselenacyclopentadecane ([15]aneSe4); tetraselenacyclohexadecane ([16]aneSe4); tetraselenacycloheptadecane ([17]aneSe4); tetraselenacyclooctadecane ([18]aneSe4); tetraselenacyclononadecane ([19]aneSe4); tetraselenacycloeicosane ([20]aneSe4); tetraselenacyclooctadiene ([8]dieneSe4); tetraselenacyclononadiene ([9]dieneSe4); tetraselenacyclodecadiene ([10]dieneSe4); tetraselenacycloundecadiene ([11]dieneSe4); tetraselenacyclododecadiene ([12]dieneSe4); tetraselenacyclotridecadiene ([13]dieneSe4); tetraselenacyclotetradecadiene ([14]dieneSe4); tetraselenacyclopentadecadiene ([15]dieneSe4); tetraselenacyclohexadecadiene ([16]dieneSe4); tetraselenacycloheptadecadiene ([17]dieneSe4); tetraselenacyclooctadecadiene ([18]dieneSe4); tetraselenacyclononadecadiene ([19]dieneSe4); tetraselenacycloeicosadiene ([20]dieneSe4); tetraselenacyclooctatetradiene ([8]tetradieneSe4); tetraselenacyclononatetradiene ([9]tetradieneSe4); tetraselenacyclodecatetradiene ([10]tetradieneSe4); and tetraselenacycloundecatetradiene ([11]tetradieneSe4).
[0697] Se Valence Stabilizer #11d: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all binding sites are composed of selenium (usually selenol or selenoether groups) and are not contained in component heterocyclic rings (Se—Se Tridentates, Se—Se Tetradentates, or Se—Se Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: hexaselenacyclododecane ([12]aneSe6); hexaselenacyclotadecane ([13]aneSe6); hexaselenacyclotetradecane ([14]aneSe6); hexaselenacyclopentadecane ([15]aneSe6); hexaselenacyclohexadecane ([16]aneSe6); hexaselenacycloheptadecane ([17]aneSe6); hexaselenacyclooctadecane ([18]aneSe6); hexaselenacyclononadecane ([19]aneSe6); hexaselenacycloeicosane ([20]aneSe6); hexaselenacycloheneicosane ([21]aneSe6); hexaselenacyclodocosane ([22]aneSe6); hexaselenacyclotricosane ([23]aneSe6); hexaselenacyclotetracosane ([24]aneSe6); hexaselenacyclododecatriene ([12]trieneSe6); hexaselenacyclotridecatriene ([13]trieneSe6); hexaselenacyclotetradecatriene ([14]trieneSe6); hexaselenacyclopentadecatriene ([15]trieneSe6); hexaselenacyclohexadecatriene ([16]trieneSe6); hexaselenacycloheptadecatriene ([17]trieneSe6); and hexaselenacyclooctadecatriene ([18]trieneSe6).
[0698] Se Valence Stabilizer #12a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of selenium and are contained in component 5-membered heterocyclic rings (Se—Se Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: tetraselenophenes; tetraselenaphospholes; tetraoxaselenoles; and tetradiselenoles.
[0699] Se Valence Stabilizer #12b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of selenium and are contained in component 5-membered heterocyclic rings (Se—Se Tridentates or Se—Se Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: hexaselenophenes; hexaselenaphospholes; hexaoxaselenoles; and hexadiselenoles.
[0700] Se Valence Stabilizer #13a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of selenium and are contained in a combination of 5-membered heterocyclic rings and selenol and selenoether groups (Se—Se Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diselenatetraselenophenes; tetraselenatetraselenophenes; diselenatetradiselenoles; and tetraselenatetradiselenoles.
[0701] Se Valence Stabilizer #13b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of selenium and are contained in a combination of 5-membered heterocyclic rings and selenol or selenoether groups (Se—Se Tridentates or Se—Se Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diselenahexaselenophenes; and triselenahexaselenophenes.
[0702] Se Valence Stabilizer #14a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of selenium and are contained in component 6-membered heterocyclic rings (Se—Se Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: tetraselenopyrans; tetraselenaphosphorins; tetraselenadiphosphorins; tetraoxaselenins; and tetradiselenins.
[0703] Se Valence Stabilizer #14b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of selenium and are contained in component 6-membered heterocyclic rings (Se—Se Tridentates or Se—Se Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: hexaselenopyrans; hexaselenaphosphorins; hexaselenadiphosphorins; hexaoxaselenins; and hexadiselenins.
[0704] Se Valence Stabilizer #15a: Examples of four-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all four binding sites are composed of selenium and are contained in a combination of 6-membered heterocyclic rings and selenol or selenoether groups (Se—Se Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diselenatetraselenopyrans; tetraselenatetraselenopyrans; diselenatetraselenaphosphorins; tetraselenatetraselenaphospborins; diselenatetraoxaselenins; tetraselenatetraoxaselenins; diselenatetradiselenins; and tetraselenatetradiselenins.
[0705] Se Valence Stabilizer #15b: Examples of six-membered macrocyclics, macrobicyclics, and macropolycyclics (including catapinands, cryptands, cyclidenes, and sepulchrates) wherein all six binding sites are composed of selenium and are contained in a combination of 6-membered heterocyclic rings and selenol or selenoether groups (Se—Se Tridentates, Se—Se Tetradentates, or Se—Se Hexadentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diselenahexaselenopyrans; triselenahexaselenopyrans; diselenahexaselenaphosphorins; triselenahexaselenaphosphorins; diselenahexaoxaselenins; triselenahexaoxaselenins; diselenahexadiselenins; and triselenahexadiselenins.
[0706] Se Valence Stabilizer #16: Examples of 1,3-diselenoketones (diseleno-beta-ketonates), 1,3,5-triselenoketones, bis(1,3-diselenoketones), and poly(1,3-diselenoketones) (Se—Se Bidentates, Se—Se Tridentates, Se—Se Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: hexafluoropentanediselenone; 1,3-diphenyl-1,3-propanediselenone; selenobenzoylselenopinacolone; diselenocyclohexoylmethane; diphenylpentanetriselenoate; tetramethylnonanetriselenoate; hexafluoroheptanetriselenoate; trifluoroheptanetriselenoate; 1-(2-thienyl)-1,3-butanediselenone, 1-(2-naphthyl)-1,3-butanediselenone, and trifluoroselenoacetylselenocamphor.
[0707] Se Valence Stabilizer #17: Examples of 1,1-diselenolates, bis(1,1-diselenolates), and poly(1,1-diselenolates) (Se—Se Bidentates and Se—Se Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: 1,1-dicyano-2,2-ethylenediselenolate; 1,1-dicarboalkoxy-2,2-ethylenediselenolate; 1,1-di(trifluoromethyl)-2,2-ethylene diselenolate; 1,1-di(pentafluorophenyl)-2,2-ethylene diselenolate; 1-pentamethylene-2,2-ethylene diselenolate; and 1-nitroethylene diselenolate.
[0708] Se Valence Stabilizer #18: Examples of diselenocarbamates, bis(diselenocarbamates), and pqly(diselenocarbamates) (including N-hydroxydiselenocarbamates and N-mercaptodiselenocarbamates) (Se—Se Bidentates, Se—Se Tridentates, and Se—Se Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: dimethyldiselenocarbamate; di(trifluorodimethyl)diselenocarbamate; diethyldiselenocarbamate; dipropyldiselenocarbamate; diisopropyldiselenocarbamate; dibutyldiselenocarbamate; ditertbutyldiselenocarbamate; dicyanamidodiselenocarbamate; azidoselenoformates; diphenyldiselenocarbamate; di(pentafluorophenyl)diselenocarbamate; dibenzyldiselenocarbamate; dinaphthyldiselenocarbamate; dicyclohexyldiselenocarbamate; dinorbornyldiselenocarbamate; diadamantyldiselenocarbamate; pyrrolidinodiselenocarbamate; piperidinodiselenocarbamate; morpholinodiselenocarbamate; thiamorpholinodiselenocarbamate; 3-pyrrolinodiselenocarbamate; pyrrolodiselenocarbamate; oxazolodiselenocarbamate; isoxazolodiselenocarbamate; thiazolodiselenocarbamate; isothiazolodiselenocarbamate; indolodiselenocarbamate; carbazolodiselenocarbamate; pyrazolinodiselenocarbamate; imidazolinodiselenocarbamate; pyrazolodiselenocarbamate; imidazolodiselenocarbamate; indazolodiselenocarbamate; and triazolodiselenocarbamate.
[0709] Se Valence Stabilizer #19: Examples of triselenophosphoric acids (phosphorotriselenoic acids), bis(triselenophosphoric acids), poly(triselenophosphoric acids), and derivatives thereof (Se—Se Bidentates, Se—Se Tridentates, Se—Se Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: triselenophosphoric acid, O-phenyltriselenophosphoric acid, O-benzyltriselenophosphoric acid, O-cyclohexyltriselenophosphoric acid, O-norbornyltriselenophosphoric acid, O,Se-diphenyltriselenophosphoric acid, O,Se-dibenzyltriselenophosphoric acid, O,Se-dicyclohexyltriselenophosphoric acid, and O,Se-dinorbornyltriselenophosphoric acid.
[0710] Se Valence Stabilizer #20: Examples of diselenophosphoric acids (phosphorodiselenoic acids), bis(diselenophosphoric acids), poly(diselenophosphoric acids), and derivatives thereof (Se—Se Bidentates, Se—Se Tridentates, Se—Se Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: diselenophosphoric acid, O-phenyldiselenophosphoric acid, O-benzyldiselenophosphoric acid, O-cyclohexyldiselenophospboric acid, O-norbornyldiselenophosphoric acid, O,)-diphenyldiselenophosphoric acid, O,O-dibenzyldiselenophosphoric acid, O,O-dicyclohexyldiselenophosphoric acid, and O,O-dinorbornyldiselenophosphoric acid.
[0711] Se Valence Stabilizer #21: Examples of tetraselenophosphoric acids (phosphorotetraselenoic acids), bis(tetraselenophosphoric acids), poly(tetraselenophosphoric acids), and derivatives thereof (Se—Se Bidentates, Se—Se Tridentates, Se—Se Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: tetraselenophosphoric acid, Se-phenyltetraselenophosphoric acid, Se-benzyltetraselenophosphoric acid, Se-cyclohexyltetraselenophosphoric acid, Se-norbornyltetraselenophosphoric acid, Se,Se-diphenyltetraselenophosphoric acid, Se,Se-dibenzyltetraselenophosphoric acid, Se,Se-dicyclohexyltetraselenopbosphoric acid, and Se,Se-dinorbornyltetraselenophosphoric acid.
[0712] Se Valence Stabilizer #22: Examples of diselenocarbonates, triselenocarbonates, bis(diselenocarbonates), and bis(triselenocarbonates), (Se—Se Bidentates and S—S Tetradentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: Se,Se-diethyldiselenocarbonate; Se Se-diisopropyldiselenocarbonate; Se,Se-diphenyldiselenocarbonate; Se,Se-dibenzyldiselenocarbonate; Se,Se-dicyclohexyldiselenocarbonate; Se,Se-dinorbornyldiselenocarbonate; diethyltriselenocarbonate; diisopropyltriselenocarbonate; diphenyltriselenocarbonate; dibenzyltriselenocarbonate; dicyclohexyltriselenocarbonate; and dinorbornyltriselenocarbonate.
[0713] Se Valence Stabilizer #23: Examples of selenocyanate ligands (Se monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn include, but are not limited to: selenocyanate (—SeCN).
[0714] Se Valence Stabilizer #24: Examples of selenolates (Se monodentates) that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: selenophenol; and naphthaleneselenol.
[0715] Miscellaneous Valence Stabilizer #1: Examples of diene, bicyclicand tricyclic hydrocarbon ligands that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: cyclopentadiene; azulene; carotene; norbornane; and adamantane.
[0716] Miscellaneous Valence Stabilizer #2: Examples of cyanide and related ligands that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: cyanide (—CN); and fulminate (—CNO).
[0717] Miscellaneous Valence Stabilizer #3: Examples of carbonyl ligands that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: carbonyl (—CO); and carbon dioxide (CO2) ligands.
[0718] Miscellaneous Valence Stabilizer #4: Examples of halogens that meet the requirements for use as “narrow band” valence stabilizers for Mn+3 and/or Mn+4 include, but are not limited to: fluorine; chlorine; bromine; and iodine.
[0719] Water-soluble precursors for the organic valence stabilizers are typically used to ensure that sufficient material is available for pigment synthesis. However, in the case of organic valence stabilizers, it is also possible to synthesize the desired MnIII or MnIV/valence stabilizer compounds from organic solvent systems. Therefore, solubility in organic solvents (for the precursors) is also acceptable. Identification of suitable water soluble precursors can be difficult because many of these organics do not form a wide range of water-soluble compounds.
[0720] 3e) Mixed Inorganic/Organic Valence Stabilizers
[0721] Mixing organic and inorganic valence stabilizers in a pigment solution will often result in a pigment with poor corrosion inhibiting properties because of cross interference. Inorganic and organic stabilizers interact with MnIII and/or MnIV in different ways. For example, inorganic valence stabilizers perform their function by forming a shell of octahedrally or square pyramidally coordinated anionic species around a captured MnIII or MnIV ion. The net charge of these inorganic MnIII- or MnIV-stabilizer compounds is therefore always negative. Organic species stabilize by the formation of a hard or soft bond between the bonding atom in the stabilizer (e.g., oxygen, nitrogen, or sulfur) and the MnIII or MnIV ion. The net charge of these compounds is usually positive. If these two very different types of stabilization ligands are combined, then the magnitude of the charge on the stabilized compound can be significantly reduced. The performance of organic or inorganic stabilized corrosion inhibitor compounds has been found to be related to the ability of the compound to form and sustain a thick electrostatic barrier layer. Additionally, a mixed stabilizer will have a poorly developed electrostatic field and a non-optimal packing around the MnIII or MnIV ion, resulting in a compound with less resistance to aqueous attack. Mixed organic/inorganic stabilized MnIII or MnIV pigments can perform more poorly than pigments that have exclusively inorganic or organic valence stabilizers for this reason.
[0722] 4) Additional Solubility Control Agents
[0723] The use of additional solubility control agents is optional. For example, the anions or cations present in the pigment synthesis bath useful for preparation of “sparingly soluble” pigments may be sufficient to form compounds with the desired solubility and saturated pH characteristics. However, pigment synthesis may produce compounds with greater than optimal solubilities, and the use of additional solubility control agents may be desirable. In situations where fine tuning of solubility or saturated pH is desired, cationic species are typical for MnIII- or MnIV-stabilizer combinations when an inorganic valence stabilizer is used, and anionic species are typical for MnIII or MnIV/organic valence stabilizer combinations.
[0724] Additional solubility and saturated pH control can be achieved through the use of nontoxic inorganic cations, which include, but are not limited to: H+, Li+, Na+, K+, Rb+, Cs+, NH4+, Mg+2, Ca+2, Sr+2, Y+3, La+3, Ce+3, Ce+4, Nd+3, Pr+3, Sc+3, Sm+3, Eu+3, EU+2, Gd+3, Tb+3, Dy+3, Ho+3, Er+3, Tm+3, Yb+3, Lu+3, Ti+4, Zr+4, Ti+3, Hf+4, Nb+5 Ta+5, Nb+4, Ta+4, Mo+6, W+6, Mo+5, W+5, Mo+4, W+4, Mn+2, Mn+3, Mn+4, Fe+2, Fe+3, Co+2, Co+3, Ru+2, Ru+3, Ru+4, Rh+3, Ir+3, Rh+2, Ir+2, PD+4, Pt+4, Pd+2, Pt+2, Cu+2, Cu+2, Cu+3, Ag+, Ag+2, Ag+3, Au+, Au2, Au+3, Zn+2, Al+3, Ga+3, Ga+, In+3, In+, Ge+4, Ge+2, Sn+2, Sn+4, Sb+3, Sb+5, Bi+3, and Bi+5. Any water-soluble compound containings these cations can be used for this purpose. The nitrates, chlorides, bromides, and perchlorates of these cations offer inexpensive water-soluble precursors, although many other water-soluble precursors exist. The use of alkaline ions such as Mg+2, Ca+2, and Sr+2 for solubility control has been demonstrated successfully, with acceptable saturated pH values.
[0725] Cationic solubility control may also be achieved through the use of nontoxic organic cations that include, but are not limited to: quaternary ammonium compounds (NR4+, where R can be any combination of alkyl, aromatic, or acyclic organic substituents, such as the methyltriethylammonium ion); organic compounds containings at least one N+ site (such as pyridinium or thiazolium cations); organic compounds containing at least one phosphonium site (P+, such as the benzyltriphenylphosphonium ion); organic compounds containing at least one stibonium site (Sb+, such as the tetraphenylstibonium ion); organic compounds containing at least one oxonium site (O+, such as pyrylium cations); organic compounds containing at least one sulfonium site (S+, such as the triphenylsulfonium ion); and organic compounds containing at least one iodonium site (I+, such as the diphenyliodonium ion).
[0726] The quaternary ammonium compounds, organic compounds containing at least one N+ site, and organic compounds containing at least one oxonium site are the most important of these classifications because of the very large number of stable cations that are available. Water-soluble precursors for these organic cations are desirable in order to maximize the amount of material available in the appropriate pigment synthesis solution. Most of these materials are also soluble in organic solvents and hydrocarbons. Fluorides, chlorides, and bromides offer the most water-soluble precursors for these organic cations, although nitrates and perchlorates of those cations with lower molecular weights (e.g., tetramethylammonium) are also acceptable water-soluble precursors. Nitrates and perchlorates of larger (greater molecular weight) organic cations are generally not acceptable as precursors because of their low water solubility.
[0727] Toxic inorganic or organic cations can be used as additional solubility control agents although this is less desirable. Examples of toxic inorganic cations that can be used include, but are not limited to: Be+2, Ba+2, V+5, V+4, V+3, Cr+3, Ni+2, Ni+4, Os+4, Cd+2, Hg+1, Hg+2, Tl+, Tl+3, As+3, As+5, Pb+2, and Pb+4. Examples of toxic organic cations include, but are not limited to: organic compounds containing at least one arsonium site (an example being the tetraphenylarsonium ion of As+) and organic compounds containing at least one selenonium site (an example being the triphenylselenonium ion of Se+). Use of these materials for additional solubility control may be necessary in some specific instances where the toxicity of the resulting pigment is of limited importance to the operator. Water-soluble precursors for these toxic cations are typical in order to maximize the amount of available cation for solubility control in aqueous-based synthesis solutions. The organic cations are frequently hydrocarbon-soluble. In general, the nitrates, chlorides, bromides, and perchlorates of these cations offer the highest water solubility.
[0728] Additional solubility control can also be achieved by using nontoxic inorganic anions, especially for MnIII or MnIV/organic valence stabilizer combinations. Soluble precursors for these inorganic anions are desirable in order to maximize the amount of material available in the appropriate pigment formation solution. Inorganic examples include, but are not limited to: fluorotitanates, chlorotitanates, fluorozirconates, chlorozirconates, fluoroniobates, chloroniobates, fluorotantalates, chlorotantalates, molybdates, tungstates, permanganates, fluoromanganates, chloromanganates, fluoroferrates, chloroferrates, fluorocobaltates, chlorocobaltates, fluorozincates, chlorozincates, borates, fluoroborates, fluoroaluminates, chloroaluminates, carbonates, silicates, fluorosilicates, fluorostannates, nitrates, nitrites, azides, phosphates, phosphites, phosphonates, phosphinites, thiophosphates, thiophosphites, thiophosphonates, thiophosphinites, fluorophosphates, fluoroantimonates, chloroantimonates, sulfates, sulfites, sulfonates, thiosulfates, dithionites, dithionates, fluorosulfates, tellurates, fluorides, chlorides, chlorates, perchlorates, bromides, bromates, iodides, iodates, periodates, and heteropolyanions (e.g., heteropolymolybdates or silicomolybdates).
[0729] Additional solubility control can also be achieved through the use of an almost unlimited number of nontoxic organic anions (e.g., organics with different carboxylate or acid groups). Examples include, but are not limited to: ferricyanides; ferrocyanides; cyanocobaltates; cyanocuprates; cyanomanganates; cyanates; cyanatoferrates; cyanatocobaltates; cyanatocuprates; cyanatomanganates; thiocyanates; thiocyanatoferrates; thiocyanatocobaltates; thiocyanatocuprates; thiocyanatomanganates; cyanamides; cyanamidoferrates; cyanamidocobaltates; cyanamidocuprates; cyanamidomanganates; nitritoferrates; nitritocobaltates; azides; (thio)carboxylates, di(thio)carboxylates, tri(thio)carboxylates, or tetra(thio)carboxylates [useful representatives including, but not limited to, acetic acid, benzoic acid, succinic acid, fumaric acid, salicylic acid, lactic acid, tartaric acid, antimonyl tartrates, cinnamic acid, adipic acid, phthalic acid, terephthalic acid, citric acid, ascorbic acid, malic acid, malonic acid, oxalic acid, stearic acid, gallic acid, naphthenic acid, camphoric acid, nitrosalicylic acid, aminosalicylic acid, acetylsalicylic acid, sulfosalicylic acid, nitrobenzoic acid, perfluoroC2-16 carboxylic acids, trinitrobenzoic acid, chlorobenzoic acid, anisic acid, iodobenzoic acid, anthranilic acid, mandelic acid, toluic acid, nicotinic acid, isonicotinic acid, pyrazolecarboxylic acid, picrolonic acid, quinaldic acid, diphenic acid, benzoquinaldic acid, quinolinecarboxylic acid, isoquinolinecarboxylic acid, triazinecarboxylic acid, (thio)carbonic acids, (thio)carbamic acids, trimethylhexylic acid, tetrafluorophthalic acid, ethylenediaminetetraacetic acid, toluoylpropionic acid, lactobionic acid, octylthiopropionate, lipoic acid, methylbenzoylpropionic acid, anthracenesuccinic acid, benzothiazolecarboxylic acid, phenylacetic acid, glycolic acid, thioglycolic acid, benzothiazolylthiosuccinic acid, benzothiazolylthiopropionic acid, phenylanthranilic acid, furancarboxylic acid, nitrofuroic acid, phosphonobutanetricarboxylic acid benzothiazolylthiosuccinic acid, N-phosphonomethylglycine, cresoxyacetic acid, aminobutyric acid, alanine, asparagine, cysteine, glutamine, glycine, leucine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, glutamic acid, aspartic acid, arginine, histidine, lysine, trihydroxyglutaric acid, phenoxyacetic acid, hydroxynaphthoic acid, phenylbutyric acid, hydroxyphosphonoacetic acid, tropic acid, aminophenylpropionic acid, dihydrocinnamic acid, hydroxycinnamic acid, cinchomeronic acid, aurintricarboxylic acid, benzotriazolecarboxylic acid, hydroxyphosphonoacetic acid, cyanuric acid, barbituric acid, violuric acid, diphenylvioluric acid, dilituric acid, thiobarbituric acid, cresotic acid, trimethylhexylic acid, nitrilotriacetic acid, N,N′-terephthaloylbis(aminocaproic acid), ethyleneglycolbis(aminoethylether)tetraacetic acid, diethylenetriaminepentaacetic acid, 2-phosphonobutanetricarboxylic acid, N,N′-bis(2-hydroxysuccinyl)ethylenediamine, nicotinic acid, naptalam, nitrobenzoic acid, nonylphenoxyacetic acid, and olsalazine]; (thio)phenolates, di(thio)phenolates, tri(thio)phenolates, or tetra(thio)phenolates [useful representatives including, but not limited to, pyrocatechol, resorcinol, picric acid, styphnic acid, pyrogallol, purpurin, purpurogallin, benzopurpurin, gallein, thiophenol, rhodizonic acid, kojic acid, chromotropic acid, carminic acid, fluorescein, tannic acid, and humic acid]; (thio)phosphonates, di(thio)phosphonates, or tri(thio)phosphonates [useful representatives including, but not limited to, diethylphosphonic acid, diphenylphosphonic acid, nitrophenylphosphonic acid, perfluoroC2-16 phosphonic acids, benzenephosphonic acid, phytic acid, hydroxyethylidenebisphosphonic acid, nitrilotrimethylenephospbonic acid, aminomethylenephosphonic acid, etidronic acid, ethylphosphonic acid, chloroethylphosphonic acid, ethylenediaminotetramethylenephosphonic acid, laurylhydroxydiphosphonic acid, methylaminodimethylenephosphonic acid, alkyl(aryl)diphosphonic acids, N-cetylaininoethanediphosphonic acid, carboxyhydroxymethylphosphonic acid (hpa), oxyethylidenediphosphonic acid, polycaproamidophosphonates, phenylethanetriphosphonic acid, oxidronic acid, and pamidronic acid]; (thio)phosphonamides, di(thio)phosphonamides, or tri(thio)phosphonamides [useful representatives including, but not limited to, phosphoramidic acid, phosphordiamidic acid (diamidophosphonic acid), and phosphoramidothioic acid]; amino(thio)phosphonates, diamino(thio)phosphonates, or triamino(thio)phosphonates; imino(thio)phosphonates or diimino(thio)phosphonates; (thio)sulfonates, di(thio)sulfonates, or tri(thio)sulfonates [useful representatives including, but not limited to, methanesulfonic acid, benzenesulfonic acid, aminobenzenesulfonic acid (sulfanilic acid), nitrobenzenesulfonic acid, phenylsulfonic acid, naphthalenesulfonic acid, nitronaphthalenesulfonic acid, oxinesulfonic acid, alizarinsulfonic acid, benzidinesulfonic acid, flavianic acid, camphorsulfonic acid, diiodophenolsulfonic acid (sozoiodol), 8-hydroxyquinoline-5-sulfonic acid, 7-nitro-8-hydroxyquinoline-5-sulfonic acid; benzotriazolesulfonic acid, bis(trifluoromethyl)benzenesulfonic acid, diiododihydroxybenzophenonesulfonic acid, p-amino-p′-ethoxydiphenylamine-o-sulfonic acid, 1-amino-2-naphthol-4-sulfonic acid; 1,2-diaminoanthraquinone-3-sulfonic acid, 1,5-dinitro-2-naphthol-7-sulfonic acid, perfluoroC2-16 sulfonic acids, benzenedisulfonic acid, phenyldisulfonic acid, naphthalenedisulfonic acid, 3,6-naphtholdisulfonic acid, indigodisulfonic acid, benzidinedisulfonic acid, carboxyiodobenzenesulfonic acids; N-benzeneaminomethanesulfonic acid (ams); amido-G-acid; amido-R-acid; naphthalene(di)sulfonic acid (Armstrong's acid); amsonic acid; Badische acid; camphorsulfonic acid; chrysophenine; Cassella's acid; chromotropic acid; Cleve's acid; croceic acid; anthracenesulfonic acid; hydroxyquinolinesulfonic acid; hydrazinobenzenesulfonic acid; indigo cannine; indoxyl; isatinsulfonic acid; indican; lignosulfonic acid; metanil yellow; metanilic acid; naphthoquinonesulfonic acid; Nuclear Fast Red; naphthol(di)sulfonic acid; naphthylamine(di)sulfonic acid; Orange I; orthanilic acid; phenol(di)sulfonic acid; methylenedinapbthalenesulfonic acid; methyl orange; and piperazinediethanesulfonic acid (pipes)]; (thio)sulfonamides, di(thio)sulfonamides, or tri(thio)sulfonamides; amino(thio)sulfonates, diamino(thio)sulfonates, or triamino(thio)sulfonates; imino(thio)sulfonates (including sulfamates) or diimino(thio)sulfonates (including disulfamates) [useful representatives including, but not limited to, methylsulfamic acid and phenylsulfamic acid]; (thio)borates, di(thio)borates, or (thio)boronates [useful representatives including, but not limited to, phenylboric acid and borotartaric acid]; organic silicates; and stibonates [useful representatives including, but not limited to, antimonyl tartrate and benzenestibonic acid]. Soluble precursors for these organic anions are desirable to maximize the amount available in the appropriate pigment synthesis solution. These organic anions are frequently soluble in organic solvents or hydrocarbons in addition to water-based systems.
[0730] Finally, toxic inorganic or organic anions can be used as additional solubility control agents, although they are less desirable. Examples of toxic inorganic anions include, but are not limited to: arsenates, arsenites, fluoroarsenates, chloroarsenates, selenates, selenites, fluorothallates, chlorothallates, iodomercury anions (e.g., Nessler's reagent), thiocyanatomercury anions (e.g., Behren's reagent), chloromercurates, bromomercurates, osmates, fluoronickelates, chromates, Reinecke's salt, and vanadates. Examples of toxic organic anions include cyanides; cyanochromates; cyanonickelates; cyanatochromates; cyanatonickelates; thiocyanatochromates; thiocyanatonickelates; cyanamidochromates; cyanamidonickelates; nitritonickelates; arsonates, diarsonates, or triarsonates [useful representatives being propylarsonic acid, phenylarsonic acid, hydroxyphenylarsonic acid, benzenearsonic acid, methylbenzenearsonic acid, hydroxybenzenearsonic acid, and nitrobenzenearsonic acid]; and organic selenates, diselenates, or triselenates. These materials may be necessary in some specific instances for additional solubility control where toxicity of the final pigment material is of limited importance. Soluble precursors for these organic anions are desirable to maximize the amount available in the appropriate pigment synthesis solution. The alkali or ammonium species of these anions typically offer the greatest water solubility.
[0731] Solubility control agents can also be used for “low solubility” and “insoluble” MnII and MnIV pigments for use as lead chromate and/or red lead replacements. However, the choice of solubility control agents is limited due to the chemistry and preparation methods for these pigments. These pigments are typically prepared by calcining, firing, or otherwise heating powder mixtures, so organic solubility control agents are not acceptable because of thermal degradation. In addition, because these calcined or fired manganese-containing mixtures result in complex oxide compounds, there is no need to add anionic solubility control agents. The only solubility control agents suitable for use with the “low solubility” or “insoluble” MnII or MnIV pigments will overwhelmingly be inorganic cations.
[0732] Solubility control agents for calcined, fired, or otherwise heated MnIII and/or MnIV-containing pigments include, but are not limited to: Li+, Na+, K+, Rb+, Cs+, Be+2, Mg+2, Ca+2, Sr+2, Ba+2, Y+3, La+3, Ce+3, Ce+4, Ti+4, Zr+4, V+5, Nb+5, Ta+5, Mo+6, W+6, Cr+3, Mn+2, Fe+3, Fe+2, Co+2, Co+3, Ni+2, Cu+2, Ag+, Ag+2, Zn+2, Al+3, In+3, Sn+4, Sb+3, Sb+5, Bi+3, and Bi+5. Table 6 shows example compositions of low solubility or insoluble MnIII or MnIV compounds suitable as pigments that can be produced for many of these solubility control cations. It is interesting to note the similarity between these compositions and those shown in Table I for naturally-occurring MnIII or MnIV minerals, further validating their longterm stability. As the solubility control cation is changed, dramatic differences in solubility can be observed. For example, Mg-containing MnIII or MnIV pigments (i.e., MgMn2O4) exhibit higher solubilities (i.e., 10−4 moles/liter MnIII or MnIV) whereas Ba-containing MnIII or MnIV pigments (i.e., BaMnO3) exhibit much lower (i.e., 10−8 or 10−9 moles/liter MnIII or MnIV) solubilities. In this way, even the performance of calcined or fired MnIII or MnIV ceramic powders can be tailored for specific applications. Combinations of these ions can also be used to modify performance.
[0733] It has been noted that one of the primary functionalities of lead chromate and especially red lead pigments is the ability to insolubilize corrosive anions (especially sulfate) via the divalent lead ion. Similar functionality can be achieved using proper choice of the solubility control agents described above. For example, barium (Ba+2) is notorious for its ability to insolubilize sulfate ions. Bismuth (Bi+3) can produce insoluble chlorides under the proper conditions. Therefore, of the cationic solubility control agents listed above for “low solubility” or “insoluble” MnIII and MnIV pigments, those containing Ba+2, Bi+3, and Bi+5 are typical.
[0734] Similarly, compositions containing cations that are themselves corrosive towards structural metals are less desirable. Hence, compositions containing potassium (K+) and especially sodium (Na+) are less desirable. 7 TABLE 6 Representative Examples of Low Solubility or Insoluble MnIII or MnIV Pigments Suitable For Lead Chromate or Red Lead Replacements Solubility Control Cation Example Composition(s) Comments None MnO2, Mn3O4, Mn2O3, No compositional modification of MnO(OH), Mn(O,OH)2 properties Lithium (Li+) LiMn2O4 Magnesium (Mg+2) MgMn2O4 Highest solubility of MgMnO3 calcined pigments MgMnO3 is unstable Solid solutions with MgAl2O4 or MgFe2O4 also possible Calcium (Ca+2) CaMnO3, CaMn2O4, CaMnO3 most stable Ca2MnO4 Solid solutions with Co, Fe, Ni, Bi, Ba, Zn, Sr, La, Ce, and Y formulas also possible Strontium (Sr+2) SrMnO3 Solid solutions with Ca, Zn, Ba, Bi, La, Ce, and Y formulas also possible Barium (Ba+2) BaMnO3, BaMn8O16 Solid solutions with Sr, Ca, Zn, Bi, La, Y, and Ce formulas also possible Zinc (Zn+2) ZnMn2O4, ZnMn3O7 Solid solutions with Co, Cu, Ni, Fe, Ca, Sr, Ba, La, Ce, Y, and Bi formulas also possible Bismuth (Bi+3) BiMnO3, BiMn2O5 Solid solutions with Ca, Sr, Ba, Zn, La, Ce, and Y formulas also possible Lanthanum (La+3) LaMnO3 Solid solutions with Sr, Ca, Zn, Ba, Ce, Bi, and Y formulas also possible Cerium (Ce+3) CeMnO3 Solid solutions with Sr, Ca, Zn, Ba, Bi, La, and Y formulas also possible Yttrium (Y+3) YMnO3 Solid solutions with Sr, Ca, Zn, Ba, Bi, La, and Ce formulas also possible Aluminum (Al+3) AlMn2O4 Exhibits higher solubility Somewhat unstable Cobalt (Co+2) CoMn2O4, CoMn3O7 Solid solutions with Ni, Fe, Zn, Cu, and Ca formulas also possible Nickel (Ni+2) NiMn2O4, NiMn3O7 Solid solutions with Co, Fe, Zn, Cu, and Ca formulas also possible Iron (Fe+2) FeMn2O4, FeMn3O7 Solid solutions with Co, Ni, Zn, Cu, and Ca formulas also possible Copper (Cu+2) CuMn2O5, CuMn3O7 Solid solutions with Zn, Co, Fe, Ni formulas also possible
[0735] 5) Valence Stabilizers for “Indicator Pigments”
[0736] Some heteropolymetallate valence stabilizers for trivalent or tetravalent manganese pigments have been observed to result in pigments that change color as the MnIII- or MnIV-stabilizer compound was exhausted during corrosion. For example, molybdate-stabilized MnIV pigments are typically moroon in color after being prepared and combined with a suitable binder system. These pigments were observed to gradually change from maroon to royal blue after extended exposure to ASTM B-117 and ASTM G-85 accelerated corrosion testing environments. The rate of color change was gradual with time and scaled with initiation and continued corrosion of the substrate. The color change from maroon to blue is well-documented in the inorganic chemistry literature for heteropolymolybdates. Numerous studies have shown that the color change associated with molybdenum blues is due to reduction of the molybdenum (VI) ion (the valence stabilizer for MnIV in this example), to the more reduced molybdenum (IV) ion. Other manganese-containing compounds can exhibit differences in color with the change in valence of the manganese ion in the pigment compound. Organometallic literature has many examples of manganese compounds where an organic trivalent or tetravalent manganese compound is one color and the divalent compound is a different color.
[0737] Color changes in the paint can be used as a metric to determine when the corrosion-inhibiting ability of the pigment has begun to fail. Alternatively, changes in pigment color hue may suggest remaining corrosion-inhibiting service life. The color change behavior is not observed for all MnIII- or MnIV-valence stabilizer combinations. Those compositions that do exhibit a significant color change between fully oxidized and reduced valence states are typical for applications where an indication of the amount of remaining unreacted pigment is desired. This represents an advantage over conventional chromate or plumbate pigments which do not demonstrate a significant color change during reduction.
[0738] B) Pigment Synthesis
[0739] The manganese compounds of the present invention can be synthesized by many different formation routes, and the synthesis of specific trivalent or tetravalent manganese compounds is often found in the general manganese coordination chemistry literature. The syntheses of several trivalent or tetravalent manganese compounds suitable for use as pigments are outlined in the Examples section of this specification.
[0740] The pigments can be synthesized via precipitation routes (including onto inorganic or organic substrates), by firing of constituents, by evaporative routes, etc. In general, “sparingly soluble” MnIII and MnIV pigments are best prepared by precipitation or evaporation routes, whereas “low solubility” or “insoluble” MnIII and MnIV pigments are best prepared by firing of constitutents. Precipitation is a typical synthesis route, for “sparingly soluble” pigments because: a) it is easiest to control, b) it allows inorganic valence stabilizers to polymerize, and c) many organic valence stabilizer precursors are degraded by high temperatures. Precipitation from aqueous (water-based) solutions is typical, because the formed trivalent or tetravalent manganese pigment materials are required to be sparingly soluble in water in order to function adequately as corrosion-inhibitors. For the more soluble pigments (i.e., with solubilities as high as 1×100 moles/liter of trivalent or tetravalent manganese, for specialized applications), precipitation can be aided by traditional salting-out methodologies, such as adding salt or alcohols to further facilitate precipitation. If desired, precipitation onto or in combination with inert materials such as oxides, hydroxides, silicates, borates, aluminates, phosphates, carbonates, titanates, molybdates, tungstates, oxalates, polymers, etc., can be initiated. An almost infinite variety of colors, hues, tints, solubilities, saturated pHs, decomposition temperatures, melting points, and corrosion-inhibiting action can be produced in pigments based solely on the MnIII or MnIV ions.
[0741] Organic solvents can also be used for the synthesis of these pigments, especially for many of the organic valence-stabilized manganese compounds. Conventional organic solvents include, but are not limited to: methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, benzyl alcohol, glycerol, ethylene glycol, propylene glycol, cresol, cycldhexanol, butyl carbitol, cellosolve, methyl cellosolve, ethyl lactate, acetone, methyl ethyl ketone (MEK), diethyl ketone, methyl isobutyl ketone (MIBK), cyclohexanone, acetophenone, diethyl ether, isopropyl ether, furan, tetrahydrofuran (THF), dioxane, tetrahydropyran, methyl formate, ethyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, propylene oxide, acetic acid, propionic acid, butyrolactone, ethylene carbonate, propylene carbonate, benzaldehyde, propyl amine, diethyl amine, ethanolamine, aniline, pyridine, acetonitrile, dimethylformamide (DMF), propionitrile, nitrobenzene, hexane, cyclohexane, benzene, toluene, xylene, carbon tetrachloride, chloroform, methylene chloride, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, Freon 1113, carbon disulfide, dimethyl sulfoxide (DMSO), and hexamethylphosphoric triamide (HMPT). These solvents can be used in instances where the specific MnIII or MnIV/valence stabilizer is insoluble in that specific solvent and sparingly soluble in water, or in instances where evaporative formation of fine particle sizes is desired.
[0742] A typical MnIV compound with-inorganic valence stabilization was prepared as follows:
[0743] 1) the stabilizer was dissolved in a minimum of water with added acetic acid or sodium acetate to buffer the solution to the proper pH;
[0744] 2) manganese nitrate was dissolved in a separate buffered water solution;
[0745] 3) the stabilizer solution was heated to near boiling and the manganese solution added all at once;
[0746] 4) this stabilizer-manganese solution was heated for 15 to 60 minutes with a potassium acetate buffer to initiate inorganic polymerization of the valence stabilizer in the presence of a persulfate oxidizer to form tetravalent manganese;
[0747] 5) this solution (mother liquor) was cooled and any precipitate filtered;
[0748] 6) the mother liquor was separated into five fractions and an additional solubility control agent was added; and
[0749] 7) each solution from step 6 was ice chilled and precipitates filtered and dried.
[0750] Solubility control agents Mg, Ca, Zn, Sr, and Ba were used to obtain a broad spectrum of solubilities with a single MnIV-valence stabilizer combination. Occasionally a precipitate would not form with the addition of a “solubility control agent” or a day of evaporation. This would imply that the target compound was extremely water soluble and unsuited for use as a pigment. Conversely, a precipitate would occasionally form immediately on addition of the last pH buffer or even the oxidizing agent. This would imply that the target MnIV compound was extremely insoluble and unsuited for use as a corrosion inhibiting pigment when incorporating the buffer or oxidizer's cations.
[0751] MnIII and MnIV pigments with organic valence stabilizers were synthesized in a similar fashion. Water-soluble organic ligands (i.e., the azo dye examples) allowed the entire synthesis to be performed in aqueous solution. Valence stabilizers of low water solubility (i.e., 8-hydroxyquinoline) were complexed in an isopropanol/water mixture. It was not necessary to carefully control pH of the organic syntheses because polymerization like that needed for the heteropolymetallate inorganic stabilizers was not necessary. Anionic “solubility control agents” such as sulfate, phosphate, molybdate, tungstate, and phosphomolybdate were used for the organic examples to form progressively larger compounds with less solubility.
[0752] The color of MnIII or MnIV pigments depends on the specific MnIII or MnIV-valence stabilizer combination. Inorganically valence stabilized MnIII or MnIV compounds ranged from maroon to black. The color of MnIII and MnIV-pigments incorporating organic valence stabilizers often matched the color of the valence stabilizer. This was particularly true of the azo dyes. The colors of the organically stabilized pigments were orange-yellow ranging to green or brown.
[0753] Oxidation of divalent manganese to the trivalent or tetravalent oxidation state can be performed prior to, or after, compound formation. If trivalent or tetravalent manganese salts are to be used for synthesis, then additional oxidation may or may not be necessary, depending upon the synthesis conditions. For example, a MnIII or MnIV/valence stabilizer coordination compound could be prepared, or a MnII/valence stabilizer compound could be prepared and subsequently oxidized to a MnIII or MnIV/valence stabilizer compound. Oxidation prior to compound formation is typical, however, to ensure that the stability of the formed compound is maintained.
[0754] The stability of compounds using the same valence stabilizer ligand differs significantly because of the difference in size between the MnII, MnIII, and MnIV ions (67 pm versus 61 pm versus 54 pm). This has to do with the size requirements of the coordinating ligand. Therefore, one ligand geometry may result in a very stable MnIII compound, but the same compound containing MnIII or MnIV can, in many instances, exhibit lower stabilities because of the difference in size of the ions. Oxidation to the trivalent or tetravalent state prior to precipitation (or other preparative methodology) ensures that once recovered, the compound is for the most part in a usable form.
[0755] Preparation of a divalent manganese compound, with subsequent oxidation treatment (e.g., via steam, gaseous oxygen, concentrated liquid oxidizer, etc.) to convert the compound to a trivalent or tetravalent oxidation state, can degrade the ligand or the entire compound, or can alter substituent groups on that ligand. Trivalent or tetravalent manganese/valence stabilizer complexes having a melting temperature lower than approximately 50° C. can be produced as a low melting solid, or a liquid-phase inhibitor. They can also be combined with inert materials in order to provide a solid material. If combination with inert materials is desired, then the trivalent or tetravalent corrosion inhibiting compound can be absorbed into, or adsorbed onto, the surfaces of the inert particles. The particles can be inorganic (e.g., oxides, hydroxides, phosphates, borates, silicates, carbonates, aluminates, titanates, molybdates, tungstates, oxalates, polymers, or combinations thereof) or organic (e.g., polymeric) in nature.
[0756] If low solubility or insoluble MnIII or MnIV compounds are desired, then calcining, heating, or firing of mixtures of compounds in an oxidizing environment represents the simplest route to formation. Firing temperatures of between about 200 and about 1200° C. typically can be used depending upon the specific composition. MnII, MnIII, MnIV, or even MnVII precursors can be used for this preparation.
[0757] Once synthesized, the pigments can then be incorporated into a wide range of binder systems to afford corrosion protection. Examples of organic binder systems that can incorporate MnIII or MnIV corrosion-inhibiting pigments include, but are not limited to: alkyd-type primers, acrylic primers, polyester primers, epoxy primers, conductive primers, organic sol-gels, ketimine coatings, polyvinyl coatings, acrylic thermoplastics, asphaltic and coal tar thermoplastics, polyamide thermoplastics, polyethylene dispersion thermoplastics, fluorocarbon thermoplastics, chlorocarbon thermoplastics, silicone thermosets, polyurethane thermosets, polyester thermosets, epoxy-amine thermosets, epoxy-amide thermosets, epoxy-ester thermosets, epoxy-coal tar thermosets, furane thermosets, phenolic thermosets, butadiene styrene elastomers, chlorinated rubber elastomers, polysulfonated elastomers, neoprene elastomers, sulfur-containing rubbers, or combinations thereof. Examples of inorganic binder systems that can incorporate MnIII or MnIV pigments include, but are not limited to: low temperature enamels, low temperature glass frits, carbonaceous coatings, zeolites, inorganic sol-gels, or combinations thereof.
EXAMPLES[0758] In order that the invention may be more readily understood, reference is made to the following examples, which are intended to illustrate the invention, but not limit the scope thereof
[0759] 1) Wash Primer Preparation
[0760] The corrosion inhibiting performance of MnIII and MnIV pigments was evaluated by incorporating them into primer paint formulations. The acid wash primer paint formulation called out in DoD-P-15328 [Primer (Wash), Pretreatment (Formulation No. 117 for Metals)] was used to test the synthesized pigments. The wash primer is composed of a resin, an acid, a corrosion inhibiting pigment, powdered talc, and carbon lampblack. The acid content of this wash primer provides a rigorous initial test of the stability and performance of the pigments. Other, more benign, polymer-based binder and resin systems might not separate the compounds based on their performance as effectively or as rapidly.
[0761] The base solution for the wash primer in this specification was prepared by mixing 88.3 grams of isopropanol, 31.3 grams of n-butanol, and 3.8 grams of deionized water with 14 grams of poly(vinyl butyral) resin (PVB) (Monsanto Butvar B-90™). PVB was used exclusively throughout testing to avoid preparation and compositional complications during analysis of pigment performance. However, the invention is not limited to the use of PVB.
[0762] Acid diluent was prepared by mixing 70 grams of 85% phosphoric acid, 63 grams of deionized water, and 247 grams of isopropanol. Finely-ground pigment powder was measured out and added to 13.74 grams of the base solution for each paint to be tested. A small amount (0.2 g) of powdered talc (magnesium silicate) “filler” was added. Lampblack was not added to these samples. These components were mixed thoroughly by hand and 3.8 g of phosphoric acid diluent added with further mixing. This rough processing allowed direct comparisons of pigment performance to be made without complications due to powder treatments, modifications, and additives.
[0763] For each pigment to be tested, the primer paint was applied onto 10 metal substrates −5 precleaned 7075-T6 and 5 precleaned 2024-T3 aluminum substrates. This is not the conventional paint application procedure for aluminum alloys. Under normal service conditions, aluminum alloys are first subjected to a hexavalent chromium-containing conversion coating prior to primer application. However, the conversion coating was omitted so that the performance of the pigment alone could be evaluated and not the synergistic effects of hexavalent chromium (in the conversion coating) or even of barrier films (in the phosphate or anodized coatings).
[0764] Multiple samples of specific pigment compositions were prepared and tested. Samples treated with zinc and strontium chromate were used as comparison standards. The chromate pigments were prepared identically to those used to test MnIII and MnIV composition variations.
[0765] 2) Corrosion Testing
[0766] PVB wash primers containing various pigment formulations were evaluated by exposing them to static salt fog (ASTM B-117) and cyclic Prohesion™ (ASTM G-85.5) accelerated corrosion tests. ASTM B-117 is a traditional corrosion “proof” test that has little relation to a real working environment. This accelerated corrosion test exposes samples to a constant salt-water fog and is a de facto test of solubility for corrosion inhibitors. B-117 does not necessarily test the ability of a corrosion inhibitor to actually inhibit corrosion. This is particularly true of inhibitors and compounds that have not been fully optimized with respect to solubility. ASTM G-85.5 (Prohesion™) is a cyclic corrosion test that more closely resembles real working environments. This accelerated corrosion test exposes samples to a cycle of fog of dilute salt and ammonium sulfate at room temperature followed by forced-air drying at an elevated temperature. This is a more realistic test of the ability of a compound to inhibit corrosion. Results of these tests can be combined to gain insight into how a particular coating or compound will perform relative to a standard as well as helping identify strengths and weaknesses in the performance of the material.
[0767] 3) Rating Method
[0768] ASTM D-1654 evaluation standard for painted or coated specimens subjected to corrosive environments was used to evaluate the performance of the coatings. After the paint dried for 24 hours, each plate was scribed with an X and the plate edges were sealed with PVC tape to eliminate corrosion edge effects.
[0769] Two visual observations are associated with this rating test. Procedure A involves a rating of the failure at the scribe—the representative creepage of corrosion away from the scribe. Procedure B involves a rating of the failure in the unscribed areas in terms of the percentage which shows corrosion coming through the film. In this way, not only the bulk corrosion-inhibiting action of a pigment through the binder can be rated, but also its “throwing power”.
[0770] 4) Comparison Examples
[0771] Zinc and strontium chromates are commercial CrVI-based pigments used extensively to provide corrosion protection to metal surfaces. These pigments were used as performance baselines to determine the effectiveness of permanganate-based pigment compositions developed using the methodology described in this specification.
[0772] Chromate pigments were precipitated from aqueous solutions and incorporated into PVB wash primer formulations so that each primer sample had the same molar quantity of hexavalent chromium. These primers were then applied to 2024-T3 and 7075-T6 aluminum alloy samples. After the-samples had dried for 24 hours, they were scribed and the-edges of each sample taped to eliminate edge effects. These samples were then exposed to 168 hours of both ASTM B-117 and G-85.5. Magnesium chromate is so soluble in aqueous solution that the resin began to cross-link immediately, even before the phosphoric acid diluent was added to the PVB pigment mixture. PVB based paints containing magnesium chromate pigments performed well initially (the first 4 days of the test) but began to degrade rapidly as the chromate was depleted. Insoluble bismuth chromate appeared to enhance the effects of corrosion and performed worse than PVB samples that contained no pigment. Zinc and strontium species with intermediate aqueous solubility provided the greatest corrosion inhibition of the chromate pigments when used in the PVB wash primer.
[0773] Table 7 presents the accelerated corrosion testing results for bare 2024-T3 and 7075-T6 aluminum alloy test panels treated with PVB combined with zinc and strontium chromate corrosion inhibiting pigments. For each pigment, the first row shows the results on 2024-T3, and the second row shows the results on 7075-T6. The zinc and strontium chromate treated samples performed well during their period of exposure as is expected from the current state-of-the-art. Minor differences in performance as a function of substrate composition were noted. 8 TABLE 7 Zinc and Strontium Chromate Pigment Accelerated Corrosion Test Results 2024-T3 7075-T6 2024-T3 7075-T6 B-117 B-117 G-85 G-85 Hours Stabilizer Proc. A Proc. B Proc. A Proc. B Proc. A Proc. B Proc. A Proc. B 168 Zn as 1.35 g 10 9 9 9 10 9 9 9 168 zinc chromate 10 9 9 9 10 9 9 9 168 Sr as 1.51 g 9 9 9 9 9 9 9 9 168 strontium chromate 9 9 9 8 9 9 9 9 168 Evaluated by using ASTM D-1654 - Painted or Coated Specimens Subjected to Corrosive Environments.
[0774] 5) MnIII and MnIV Pigments in PVB Resin
[0775] MnIII- and MnIV-valence stabilizer compounds were synthesized using either published literature procedures, or standard organometallic synthesis techniques because optimized MnIII and MnIV corrosion-inhibiting pigment materials are not commercially available. The pigment syntheses were mainly aqueous-based precipitation techniques, although some pigments (i.e., those using some selected organic valence stabilizers) needed alcohol/water mixtures for the synthesis due to the low solubility of the valence stabilizer compound in pure water. Table 8 shows the MnIII- and MnIV-valence stabilizer combinations used for these optimized manganese-containing paints. As can be seen in Table 8, MnIII and MnIV pigments containing both inorganic and organic valence stabilizers were formed. 9 TABLE 8 Optimized Trivalent and Tetravalent Manganese Pigments Prepared Synthesis Addendum Pigment Solvent Ions Synthesis Notes Mn+3/phosphotungstate H2O Sr, Ca Other salts (Mg, Ba, & [11-tungstophospho- Zn) not formed manganate(III)] Mn+3/molybdate [9- H2O Mg, Ca, Zn, Sr, Ba All salts readily formed. molybdo-manganate(III)] Mn+3/iodate [Hexaiodato- H2O H, Ca, Zn, Sr, Ba H (acid) salt precip. from manganate(III)] mother liq.; precip. of Ca, Zn, Sr, and Ba salts; Mg salt not formed Mn+3/vanadate [3- H2O Na, Mg, Ca, Zn, Sr, Na salt precip. from vanado-manganate(III)] Ba mother liq. Mn+3/Diethyldithio- H2O SO4−2, PO4−3, WO4−2, MoO4−2, phoshomolybdate Mn+3/2-Mercapto- i-PrOH/H2O SO4−2 SO4−2 fm. from mother liq. benzimidazole Mn+3/8-Hydroxy- i-PrOH/H2O SO4−2, PO4−3 SO4−2 fm. from mother guinoline liq.; PO4−3 on anion addn.
[0776] Table 9 presents the accelerated corrosion testing results for bare 2024-T3 and 7075-T6 aluminum alloy test panels treated with inorganically stabilized MnIII and MnIV pigments in PVB, while Table 10 shows some organically stabilized manganese pigments. Table 9 shows the samples that were produced, as well as the pigment contained within them. Note that the molar concentration of MnIII or MnIV in these paints is much less than that in the zinc chromate primers (7.44×10−3 M). This was done because the molecular weight of the MnIII or MnIV compounds exceeds that of zinc chromate, implying that a much larger mass would be necessary to achieve equal molar concentrations of MnIII or MnIV and CrVI. As can be seen in the corrosion exposure results, even with these much lower molar concentrations of MnIII or MnIV, the “optimized” pigments provided comparable or substantial corrosion protection compared to chromium. These pigments also outperformed by a significant margin those pigments (i.e., molybdates, tungstates, phosphates, borates, cyanamides) containing no inheremt oxidizer properties. For each pigment, the first row shows the performance of one sample under the specified conditions, and the second shows the performance of a duplicate sample under the same conditions. It is also interesting to note the change in performance for the MnIII/MnIV pigments just by altering the solubility control agents. 10 TABLE 9 Inorganically Stabilized MnIII and Mn IV Wash Primers Formulations Stabilizer Inhibitor B-117 B-117 G-85 G-85 Solubility Control Agent Conc. (M) Proc. A Proc. B Proc. A Proc. B Hours Ca as 1.42 g calcium 7.44 × 10−4 6 3 5 4 6 5 7 6 117 9-molybdomanganate (10% of Cr) 6 3 5 4 6 5 7 6 117 Zn as 1.48 g zinc 7.44 × 10−4 5 3 5 4 7 7 7 7 117 9-molybdomanganate (10% of Cr) 5 3 5 3 7 6 8 7 117 Sr as 1.53 g strontium 7.44 × 10−4 5 — 4 — 6 5 6 5 117 9-molybdomanganate (10% of Cr) 5 — 5 — 6 5 6 5 117 Ba as 1.64 g barium 1.64 × 10−4 4 — 3 — 7 6 8 7 117 9-molybdomanganate (10% of Cr) 4 — 3 — 7 6 7 6 117 Ba as 2.06 g barium 1.49 × 10−3 5 3 5 3 7 7 8 8 144 hexaiodatomanganate (20% of Cr) 5 3 5 3 8 8 7 7 144 Mg as 1.28 g 7.44 × 10−4 9 7 7 8 7 6 6 5 139 magnesium (10% of Cr) 13-vanadatomanganate 9 7 7 8 7 6 7 6 139 Ca as 1.32 g calcium 7.44 × 10−4 8 7 7 6 7 6 7 6 139 13-vanadatomanganate (10% of Cr) 8 7 7 6 7 6 7 6 139 Zn as 1.37 g zinc 7.44 × 10−4 8 9 7 8 7 6 7 6 139 13-vanadatomanganate (10% of Cr) 8 9 7 8 7 5 6 5 139 Sr as 1.42 g strontium 7.44 × 10−4 7 6 7 6 6 5 6 5 139 13-vanadatomanganate (10% of Cr) 7 6 7 6 6 6 6 6 139 Ba as 1.53 g barium 7.44 × 10−4 7 8 7 6 6 6 6 5 139 13-vanadatomanganate (10% of Cr) 7 7 7 6 7 6 6 5 139 Evaluated by using ASTM D-1654 - Painted or Coated Specimens Subjected to Corrosive Environments.
[0777] 11 TABLE 10 Organically Stabilized MnIII and Mn IV Wash Primers Formulations Stabilizer/ Inhibitor B-117 B-117 G-85 G-85 Solubility Control Agent Conc. (M) Proc. A Proc. B Proc. A Proc. B Hours Mn+4/DEDT/ 1.49 × 10−3 6 5 7 6 168 sulfate (20% of Cr) 6 5 7 5 168 Mn+4/DEDT/ 1.49 × 10−3 7 5 8 7 168 phosphate (20% of Cr) 7 5 8 7 168 Mn+4/DEDT/ 1.49 × 10−3 7 6 7 5 168 molybdate (20% of Cr) 7 6 7 5 168 Mn+4/DEDT/ 1.49 × 10−3 7 5 7 5 168 tungstate (20% of Cr) 7 5 7 5 168 Mn+3/MBI/ 1.49 × 10−3 7 7 6 6 168 sulfate (20% of Cr) 8 7 6 6 168 Mn+3/HQ/ 1.49 × 10−3 6 5 6 5 168 sulfate (20% of Cr) 6 5 6 5 168 Mn+3/HQ/ 1.49 × 10−3 7 6 8 7 168 phosphate (20% of Cr) 7 6 8 7 168 Evaluated by using ASTM D-1654 - Painted or Coated Specimens Subjected to Corrosive Environments. DEDT = diethyldithiocarbamate, MBI = mercaptobenzimidazole, HQ = hydroxyquinoline
[0778] Table 10 shows the results for a few of the organic valence stabilizers evaluated. Due to low substrate supplies, these pigments were only tested on duplicate 2024-T3 aluminum alloy under both ASTM B-117 and G-85 conditions. The molar concentration of MnIII and MnIV in these pigments were also much less than in the standard chromate pigments. Clear progressions in the performance of these pigments as a function of anionic solubility control agents were also observed.
[0779] 6) Calcined MnIII and MnIV Pigments
[0780] Calcined MnIII and MnIV pigments were prepared by mixing oxides, hydroxides, or peroxides of Mg, Ca, Sr, Ba, Zn, Bi, Co, Ni, or Fe with manganese oxides such as Mn2O3 or MnO2 and firing in air for up to four hours between 400 and 715° C.±10° C. The ceramic oxide pigments were mixed 1:1 by weight with boiled linseed oil. This mixture was painted on to bare 1008 carbon steel sheet that had been prepared with an alkaline cleaning treatment. An identical steel specimen was painted with red-lead (Pb3O4) and boiled linseed for use as a comparison standard. The painted test panels were allowed to dry for 48 hours, X scribed completely through the coating, and then exposed to ASTM B 117 for 41 hours.
[0781] The Ca-, Zn-, and Sr-containing pigments demonstrated corrosion inhibition performance equal to that of the of the red lead pigments in a side by side comparison. The Ba-containing pigment performed nearly as well as Ca, Zn, and Sr formulations by providing a high degree of surface protection but not quite as good as the red lead standard.
[0782] Chromium- or lead-free pigments based on MnIII and/or MnIV which can be used as replacements for the current CrVI or PbIV pigments can be made. Many synthesis methodologies and procedures are available for those skilled in the art of coordination compound synthesis to produce a multitude of MnIII and/or MnIV corrosion inhibiting pigments. One or two synthesis procedures or solvents are likely to be typical for specific MnIII- or MnIV-valence stabilizer combinations. The methodology described in this specification encompasses the entire range of valence stabilized MnIII or MnIV pigment formulations.
[0783] Pigments formed in accordance with the prior art are not competitive with the present invention. Prior art embodiments require the use of application processes and chemical compounds that do not form pigments containing valence stabilized MnIII- or MnIV-based active corrosion inhibitors that perform equivalent to current effective commercial hexavalent chromium- or tetravalent lead-based pigment systems.
[0784] While the invention has been described by reference to certain embodiments, it should be understood that numerous changes could be made within the spirit and scope of the inventive concepts described. Accordingly, it is intended that the invention not be limited to the disclosed embodiments, but that it have the full scope permitted by the language of the following claims.
Claims
1. A corrosion-inhibiting pigment comprising manganese, wherein the manganese is trivalent manganese, tetravalent manganese, or combinations thereof, and a valence stabilizer combined to form a manganese/valence stabilizer complex.
2. The pigment of claim 1 wherein the manganese/valence stabilizer complex has a solubility in water of between about 1×100 and about 1×10−17 moles per liter of manganese at about 25° C. and about 760 Torr.
3. The pigment of claim 2 wherein the solubility of the manganese/valence stabilizer complex in water is between about 1×10−1 and about 1×104 moles per liter of manganese at about 25° C. and about 760 Torr.
4. The pigment of claim 2 wherein the solubility of the manganese/valence stabilizer complex in water is between about 1×10−6 and about 1×10−8 moles per liter of manganese at about 25° C. and about 760 Torr.
5. The pigment of claim 2 wherein the solubility of the manganese/valence stabilizer complex in water is between about 1×10−9 and about 1×10−7 moles per liter of manganese at about 25° C. and about 760 Torr.
6. The pigment of claim 1 wherein there is an electrostatic barrier layer around the manganese/valence stabilizer complex in aqueous solution.
7. The pigment of claim 1 wherein the manganese/valence stabilizer complex acts as an ion exchange agent towards corrosive ions.
8. The pigment of claim 1 wherein the manganese/valence stabilizer complex decomposes above about 100° C.
9. The pigment of claim 1 wherein the manganese/valence stabilizer complex melts above about 50° C.
10. The pigment of claim 1 wherein the valence stabilizer is an inorganic valence stabilizer or an organic valence stabilizer.
11. The pigment of claim 10 wherein the valence stabilizer is the inorganic valence stabilizer selected from molybdates, tungstates, vanadates, niobates, tantalates, tellurates, periodates, iodates, antimonates, stannates, sulfates, polyphosphates, titanates, zirconates, oxygen, bismuthates, germinates, carbonates, arsenates, phosphates, borates, aluminates, silicates, or combinations thereof.
12. The pigment of claim 1 wherein the valence stabilizer is the inorganic valence stabilizer selected from molybdates, tungstates, vanadates, niobates, tantalates, tellurates, periodates, iodates, oxygen, antimonates, stannates, sulfates, polyphosphates, titanates, zirconates, phosphates, borates, aluminates, silicates, or combinations thereof.
13. The pigment of claim 1 wherein the manganese/valence stabilizer complex has a central cavity containing a manganese ion and an additional ion.
14. The pigment of claim 13 wherein the additional ion is B+3, Al+3, Si+4, P+5, Ti+4, V+5, V+4, Cr+6, Cr+3, Mn+2, Fe+3, Fe+2, Co+2, Co+3, Ni+2, Ni+3, Ni+4, Cu+2, Cu+3, Zn+2, Ga+3, Ge+4, As+5, As+3, Zr+4, or Ce+4.
15. The pigment of claim 10 wherein the valence stabilizer is the organic valence stabilizer selected from monoamines; diamines; triamines; tetraamines; pentamines; hexamines; five- or six-membered heterocyclic rings containing one to four nitrogen atoms optionally having additional nitrogen, sulfur, or oxygen binding sites; five- or six-membered heterocyclic rings containing one or two sulfur atoms and having additional nitrogen binding sites; five- or six-membered heterocyclic rings containing one or two oxygen atoms and having additional nitrogen binding sites; (two-, three-, four-, six-, eight-, or ten-)membered nitrogen, nitrogen-sulfur, or nitrogen-oxygen macrocyclics; macrocyclic oligothioketones or dithiolenes; diazenes; thio-, amido-, or imido-derivatives of hypophosphoric, phosphoric, or diphosphoric acids and salts; thio-derivatives of hypophosphoric, phosphoric, or diphosphoric acids and salts; azo compounds, triazenes, formazans, azines, hydrazones, or Schiff Bases containing at least two azo, imine, or azine groups; azo compounds, triazenes, formazans, azines, hydrazones, or Schiff Bases; ortho- (for aryl) or alpha- or beta- (for alkyl) substituted azo compounds, triazenes, formazans, azines, hydrazones, or Schiff Bases; oximes; amidines and imido compounds; dithio ligands; amides; amino acids; N-(thio)acyl 7-aminobenzylidenimines; (thio)hydroxamates; alpha- or ortho-aminothio(di)carboxylic acids and salts; (thio)semicarbazones; (thio)acyl hydrazones; (thio)carbazones; silylaminoalcohols; thioalkyl amines and imines; hydroxyalkyl imines; (thio)aryl amines and imines; guanylureas; guanidinoureas; 2-nitrosophenols; 2-nitrophenols; N-nitrosohydroxylamines; 1,3-monothioketones; monothiomalonamides; 2-thioacylacetamides; 2-acylthioacetamides; dithiodicarbonic diamides; trithiodicarboxylic acids and salts; monothiocarbamates; monothioethers; dithioethers; trithioethers; tetrathioethers; pentathioethers; hexathioethers; disulfides; monophosphines; diphosphines; triphosphines; tetraphosphines; pentaphosphines; hexaphosphines; five- or six-membered heterocyclic rings containing one or two sulfur atoms optionally having additional sulfur, oxygen, or phosphorus binding sites; five- or six-membered heterocyclic rings containing one to three phosphorus atoms optionally having additional phosphorus, nitrogen, oxygen, or sulfur binding sites; five- or six-membered heterocyclic rings containing one to four nitrogen atoms and having additional phosphorus binding sites; five- or six-membered heterocyclic rings containing one or two oxygen atoms and optionally having additional sulfur or phosphorus binding sites; (five-, seven-, or nine-)membered nitrogen, nitrogen-sulfur, or nitrogen-oxygen macrocyclics; (two- to ten-)membered sulfur, sulfur-oxygen, or sulfur-phosphorus macrocyclics, not including oligothioketones or dithiolenes; (two- to ten-)membered phosphorus, nitrogen-phosphorus, or oxygen-phosphorus macrocyclics; (two- to ten-)membered oxygen macrocyclics; thio-, amido-, or imido-derivatives of phosphonic and diphosphonic acids and salts containing no sulfur binding sites; amido-, or imido-derivatives of hypophosphoric, phosphoric, or diphosphoric acids and salts containing no sulfur binding sites; dithioperoxydiphosphoramides; dithioperoxydiphosphoric acids and salts; monothioperoxydiphosphoramides; monothioperoxydiphosphoric acids and salts; monothiophosphoric acids; phosphoro(dithioperoxoic) acids and salts; azo compounds, triazenes, formazans, azines, or Schiff Bases; silylamines; silazanes; guanidines and diguanidines; pyridinaldimines; hydrazones; hydramides; nitriles; thioureas and thioamides; ureas and pseudoureas; biurets; monothio ligands; diketone ligands; dithioperoxydicarbonic acids and salts; dithioacyl disulfides; tetrathioperoxydicarbonic diamides; (hexa-, penta-, or tetra-)thioperoxydicarbonic acids and salts; 1,2-dithiolates; rhodanines; dithiocarbimates; (thio)xanthates; S-(alkyl- or aryl-thio)thiocarboxylic acids and salts; phosphinodithioformates; (thio)borates and (thio)boronates; (thio)arsonic acids and salts; (thio)antimonic acids and salts; phosphine and arsine sulfides or oxides; beta-hydroxyketones and aldehydes; squaric acids and salts; carbonates; carbamates and carbimates; carbazates; imidosulfurous diamides; sulfurdiimines; thiocarbonyl and mercapto oximes; 2-nitrothiophenols; 2-nitrilo(thio)phenols; acylcyanamides; imidates; 2-amidinoacetates; beta-ketoamines; 3-aminoacrylamides and 3,3-diaminoacrylamides; 3-aminoacrylic acids and salts and 3-hydroxy-3-aminoacrylic acids and salts; 2-nitroanilines; amine and diazine N-oxides; hydrazides and semicarbazides; (amino- or imino-)aryl phosphines; (thio- or hydroxy-)aryl phosphines; arsines; five- or six-membered heterocyclic rings containing one arsenic atom optionally having additional arsenic binding sites;(two- to six-)membered arsenic macrocyclics; selenoethers; five- or six-membered heterocyclic rings containing one or two selenium atoms optionally having additional selenium binding sites; (two- to six-)membered selenium macrocyclics; 1,3-diselenoketones; 1,1-diselenolates; diselenocarbamates; selenophosphoric acids and salts; selenocarbonates; cyanide, isocyanide, and cyanamide ligands; nitrosyl and nitrite ligands; azide ligands; thiolates and selenolates; (thio)cyanate ligands; diene or bicyclic or tricyclic hydrocarbon ligands; carbonyl, halogen, oxo, and hydroxo ligands; or combinations thereof.
16. The pigment of claim 15 wherein the organic valence stabilizer is selected from monoamines; diamines; triamines; tetraamines; pentamines; hexamines; five- or six-membered heterocyclic rings containing one to four nitrogen atoms optionally having additional nitrogen, sulfur, or oxygen binding sites; five- or six-membered heterocyclic rings containing one or two sulfur atoms and having additional nitrogen binding sites; five- or six-membered heterocyclic rings containing one or two oxygen atoms and having additional nitrogen binding sites; (two-, three-, four-, six-, eight-, or ten-)membered nitrogen, nitrogen-sulfur, or nitrogen-oxygen macrocyclics; macrocyclic oligothioketones or dithiolenes; diazenes; thio-, amido-, or imido-derivatives of hypophosphoric, phosphoric, or diphosphoric acids and salts; azo compounds, triazenes, formazans, azines, hydrazones, or Schiff Bases containing at least two azo, imine, or azine groups; azo compounds, triazenes, formazans, azines, hydrazones, or Schiff Bases; ortho- (for aryl) or alpha- or beta- (for alkyl) substituted azo compounds, triazenes, formazans, azines, hydrazones, or Schiff Bases; oximes; amidines and imido compounds; dithio ligands; amides; amino acids; N-(thio)acyl 7-aminobenzylidenimines; (thio)hydroxamates; alpha- or ortho-aminothio(di)carboxylic acids and salts; (thio)semicarbazones; (thio)acyl hydrazones; (thio)carbazones; silylaminoalcohols; thioalkyl amines and imines; hydroxyalkyl imines; (thio)aryl amines and imines; guanylureas; guanidinoureas; biurets; diketone ligands; amido- or imido-derivatives of hypophosphoric, phosphoric, or diphosphoric acids and salts; beta-hydroxyketones and -aldehydes; squaric acids and salts; carbamates and carbimates; 2-nitrosophenols; 2-nitrophenols; N-nitrosohydroxylamines; 1,3-monothioketones; monothiomalonamides; 2-thioacylacetamides; 2-acylthioacetamides; dithiodicarbonic diamides; trithiodicarboxylic acids and salts; monothiocarbamates; (thio)cyanate ligands; oxo and hydroxo ligands; or combinations thereof.
17. The pigment of claim 15 wherein the organic valence stabilizer is the diazene selected from diazeneformimidamides, diazeneformamides, diazenefonmothioamides, diazeneacetimidamides, diazeneacetothioamides, diazeneformimidic acids and salts, diazeneacetimidic acids and salts, diazenecarbothioic acids and salts, diazenecarbodithioic acids and salts, diazeneformimidothioic acids and salts, diazeneformaldehydes, diazeneformothioaldehydes, diazeneacetaldehydes, diazeneacetothioaldehydes, diazenediformamides, diazenediformothioamides, diazenediacetamides, diazenediacetothioamides, diazeneacetimidothioic acids and salts, imidoyldiazenes, diazenediformimidamides, diazenediacetimidamides, diazenediformimidic acids and salts, diazenediacetimidic acids and salts, diazenediformimidothioic acids and salts, diazenediacetimidothioic acids and salts, diazenedicarbothioic acids, diazenedicarbodithioic acids, diazeneformic acids, diazenediformic acids, diazeneacetic acids, diazenediacetic acids, diazenediformaldehydes, diazenediformothioaldehydes, diazenediacetaldehydes, diazenediacetothioaldehydes, diimidoyldiazenes, or combinations thereof.
18. The pigment of claim 15 wherein the organic valence stabilizer is the thio-, amido-, or imido-derivative of hypophosphoric, phosphoric, or diphosphoric acids and salts selected from phosphoramidimidic triamides, phosphoramidimidic acids and salts, phosphorodiamidimidic acids and salts, phosphorodiamidimidothioic acids and salts, phosphoramidimidothioic acids and salts, phosphorodiamidimidodithioic acids and salts, phosphoramidimidodithioic acids and salts, (di- or mono-)thiohypophospboric acids and salts, (di- or mono-)thiohypophosphoramides, phosphoramidic acids and salts, phosphorimidic acids and salts, (di- or mono-)thioimidodiphosphoric acids and salts, (di- or mono-)thiohydrazidodipbosphoric acids and salts, (di- or mono-)thioimidodiphosphoramides, (di- or mono-)thiohydrazidodiphosphoramides, phosphoric triamides, (di- or mono-)thiodiphosphoramides, (di- or mono-)thiodiphosphoric acids and salts, (tetra-, tri-, di-)thiophosphoric acids and salts, phosphoro(dithioperoxo)(mono-,di-, or tri-)thioic acids and salts, phosphorimido(mono-, di-, or tri-)thioic acids and salts, phosphorothioic triamides, phosphoramido(mono, di- or tri-)thioic acids and salts, phosphorodiamido(mono, di- or tri-)thioic acids and salts, or combinations thereof.
19. The pigment of claim 15 wherein the organic valence stabilizer is a substituent for the ortho- (for aryl) or alpha- or beta- (for alkyl) substituted azo compounds, triazenes, formazans, azines, hydrazones, or Schiff Bases selected from amino, imino, oximo, diazeno, hydrazido, thiol, mercapto, thiocarbonyl, hydroxy, carbox, and carbonyl substituents, or combinations thereof.
20. The pigment of claim 15 wherein the organic valence stabilizer is the oxime selected from monooximes, dioximes, carbonyl oximes, imine oximes, hydroxy oximes, amino oximes, amido oximes, hydrazone oximes, azo oximes, or combinations thereof.
21. The pigment of claim 15 wherein the organic valence stabilizer is the amidine and imido compound selected from amidines, diamidines, biguamides, biguanidines, diamidinomethanes, imidoylguanidines, amidinoguanidines, diformamidine oxides, sulfides, and disulfides, imidodicarbonimidic acids and salts, diimidodicarbonimidic acids and salts, thioimidodicarbonimidic acids and salts, thiodiimidodicarbonimidic acids and salts, diimidoylimines, diimidoylhydrazides, imidosulfamides, diimidosulfamides, O-amidinocarbamates, O- or S-amidino(mono-, di-, or peroxy-)thiocarbamates, N-hydroxy(or N,N′-dihydroxy)amidines, diimidosulfuric acids and salts, or combinations thereof.
22. The pigment of claim 15 wherein the organic valence stabilizer is the dithio ligand selected from dithioimidodialdehydes, dithiohydrazidodialdehydes, dithioimidodicarbonic acids and salts, dithiohydrazidodicarbonic acids and salts, 1,3-dithioketones, 1,2-dithioketones, dithiomalonamides, 2-thioacylthioacetamides, dithioacyl sulfides, trithiodicarbonic diamides, (penta-, tetra-, tri-)thiodicarbonic acids and salts, beta-mercaptothioketones and -aldehydes, N-(aminomethylthiol)thioureas, dithiooxamides, 1,1-dithiolates, (di- or per-)thiomonocarboxylic acids and salts, (tetra- or per-)thiodicarboxylic acids and salts, (di-, tri-, or per-)thiocarbonates, dithiocarbamates (including N-hydroxydithiocarbamates and N-mercaptodithiocarbamates), dithiocarbazates, or combinations thereof.
23. The pigment of claim 15 wherein the organic valence stabilizer is the amide selected from monoamides, lactams, amidinoamides, guanidinoamides, imidoylamides, polyamides, polylactams, or combinations thereof.
24. The pigment of claim 15 wherein the organic valence stabilizer is the thio-, amido-, or imido-derivative of phosphonic and diphosphonic acids and salts selected from phosphonitrile amides, phosphonimidic diamides, phosphonamidimidic acids and salts, phosphonamidimidothioic acids and salts, dithioimidodiphosphonic acids and salts, dithiohydrazidodiphosphonic acids and salts, dithioimidodiphosphonamides, dithiohydrazidodiphosphonamides, dithiodiphosphonamides, dithiodiphosphonic acids and salts, dithioperoxydiphosphonamides, dithioperoxydiphosphonic acids and salts, (di- and tri-)thiophosphonic acids and salts, phosphono(dithioperoxo)thioic acids and salts, phosphono(dithioperoxo)dithioic acids and salts, phosphonimidothioic acids and salts, phosphonimidodithioic acids and salts, phosphonothioic acids and salts, phosphonanidothioic acids and salts, phosphonamidimidodithioic acids and salts, monothioimidodiphosphonic acids and salts, monothiohydrazidodiphosphonic acids and salts, monothioimidodiphosphonamides, monothiohydrazidodiphosphonamides, monothiodiphosphonamides, monothiodiphosphonic acids and salts, monothioperoxydiphosphonamides, monothioperoxydiphosphonic acids and salts, monothiophosphonic acids and salts, phosphono(dithioperoxoic) acids and salts, or combinations thereof.
25. The pigment of claim 15 wherein the organic valence stabilizer is the amido- or imido-derivative of hypophosphoric, phosphoric, or diphosphoric acids and salts containing no sulfur binding sites selected from hypophosphoric acids and salts, hypophosphoramides, imidodiphosphoric acids and salts, hydrazidodiphosphoric acids and salts, imidodiphosphoramides, hydrazidodiphosphoramides, diphosphoramides, or combinations thereof.
26. The pigment of claim 15 wherein the organic valence stabilizer is the amido- or imido-derivative of phosphonic or diphosphonic acids and salts containing no sulfur binding sites selected from imidodiphosphonic acids and salts, hydrazidodiphosphonic acids and salts, imidodiphosphonamides, hydrazidodiphosphonamides, diphosphonamides, phosphonimidic acids and salts, phosphonamidic acids and salts, phosphonic diamides, or combinations thereof.
27. The pigment of claim 15 wherein the organic valence stabilizer is the thiourea and thioamide selected from thioureas, thiocarboxamides, thioacylthioureas, acylthioureas, thioacylureas, thioaroylthioureas, aroylthioureas, thioaroylureas, thioimidates, thioguanylureas, guanidinothioureas, amidinothioamides, guanidinothioamides, imidoylthioamides, 3-aminothioacrylamides, thiohydrazides, thiosemicarbazides, (mono- and di-)thiobiurets, (mono- and di-)thioisobiurets, (mono- and di-)thiobiureas, N-(aminomethylol)thioureas, N-(aminomethylthiol)ureas, beta-mercaptocarboxamides, or combinations thereof.
28. The pigment of claim 15 wherein the organic valence stabilizer is the biuret selected from biurets, triurets, isobiurets, biureas, triureas, acylureas, aroylureas, N-(aminomethylol)ureas, or combinations thereof.
29. The pigment of claim 15 wherein the organic valence stabilizer is the monothio ligand selected from beta-aminothiones, 3-aminothioacrylic acids and salts, 3-mercapto-3-aminothioacrylic acids and salts, N-thioacyl benzylidenimines, thioimidodialdehydes, thiohydrazidodialdehydes, thioimidodicarbonic acids and salts, thiohydrazidodicarbonic acids and salts, 1,2-monothioketones, trithioperoxydicarbonic diamides, dithioperoxydicarbonic diamides, dithiodicarbonic acids and salts, trithioperoxydicarbonic acids and salts, beta-hydroxythioketones, beta-hydroxythioaldehydes, beta-mercaptoketones, beta-mercaptoaldehydes, monothiooxamides, beta-mercaptocarboxylic acids and salts, beta-mercaptothiocarboxylic acids and salts, beta-hydroxythiocarboxylic acids and salts, S-alkylthiocarboxylic acids and salts, S-arylthiocarboxylic acids and salts, S-alkyldisulfidocarboxylic acids and salts, S-aryldisulfidocarboxylic acids and salts, monothiomonocarboxylic acids and salts, dithiodicarboxylic acids and salts, monothiocarbonates, monothiocarbazates, monothiocarbimates, mercaptoalcohols, silylmercaptoalcohols, or combinations thereof.
30. The pigment of claim 15 wherein the organic valence stabilizer is the diketone ligand selected from imidodialdehydes, hydrazidodialdehydes, imidodicarbonic acids and salts, hydrazidodicarbonic acids and salts, imidodisulfamic acids and salts, imidodisulfuric acids and salts, 1,3-diketones, 1,3,5-triketones, 1,2-diketones, 1,2,3-triketones, tropolonates, ortho-quinones, malonamides, 2-acylacetamides, monothiodicarbonic diamides, monothiodicarbonic acids and salts, trithionic acids and salts, oxamides, dicarboxylic acids, or combinations thereof.
31. The pigment of claim 15 wherein the organic valence stabilizer is the S-(alkyl- or aryl-thio)thiocarboxylic acid and salt selected from S-(alkylthio)thiocarboxylic acids and salts, S-(arylthio)thiocarboxylic acids and salts, S,S-thiobisthiocarboxylic acids and salts, S-(alkyldisulfido)thiocarboxylic acids and salts, S-(aryldisulfido)thiocarboxylic acids and salts, S,S′-disulfidobisthiocarboxylic acids and salts, or combinations thereof.
32. The pigment of claim 15 wherein the organic valence stabilizer is the phosphine and arsine sulfide or oxide selected from phosphine P-sulfides, aminophosphine sulfides, arsine As-sulfides, aminoarsine sulfides, phosphine P-oxides, aminophosphine oxides, arsine As-oxides, aminoarsine oxides, or combinations thereof.
33. The pigment of claim 15 wherein a solubility in water of the manganese/valence stabilizer complex is adjusted by an addition of a substituent group on the organic valence stabilizer.
34. The pigment of claim 33 wherein the solubility in water is increased by the addition of the substituent group selected from sulfonate groups (—SO3−), carboxyl groups (—CO2—), hydroxyl groups (—OH), ester groups (—CO3—), carbonyl groups (═C═O), amine groups (—NH2), nitrosamine groups (═N—N═O), carbonylnitrene groups (—CO—N), sulfoxide groups (═S═O), sulfone groups (═S[═O]2), sulfinyl groups (—N═S═O), sulfodiimines (═S[=NH]2), sulfonyl halide groups (—S[═O]2X), sulfonamide groups (—S[═O]2NH2), monohalosulfonamide groups (—S[═O]2NHX), dihalosulfonamide groups (—S[═O]2MX2), halosulfonate groups (—S[═O]2OX), halosulfonate amide groups (═N—S[═O]2X), aminosulfonate groups (═N—S[═O]2OH), iminosulfonate groups (—N[SO3−]1-2), phosphonate groups (PO3−2), phosphonamide groups (—PO2NH2−), phosphondiamide groups (—PO[NH2]2), aminophosphonate groups (═N—PO3−2), iminophosphonate groups (—N[PO3−2]1-2), or combinations thereof.
35. The pigment of claim 33 wherein the solubility in water is decreased by the addition of the substituent group selected from nitro groups (—NO2), perfluoroalkyl groups (—CxF2x+1), perchloroalkyl groups (—CxCl2x+1), nitramine groups (═N—NO2), thioketone groups (═C═S), sulfenyl halide groups (—S—X), sulfur dihaloimide groups (—N═SX2), or combinations thereof.
36. The pigment of claim 15 wherein an electrostatic barrier layer of the manganese/valence stabilizer complex is adjusted by an addition of a substituent group on the organic valence stabilizer.
37. The pigment of claim 36 wherein the electrostatic barrier layer is increased by the addition of the substituent group selected from ketones (═C═O), thioketones (═C═S), amides (—C[═O]NR2), thioamides (—C[═S]—NR2), nitriles or cyano groups (—CN), isocyanides (—NC), nitroso groups (—N═O), thionitroso groups (—N═S), nitro groups (—NO2), azido groups (—N3), cyanamide or cyanonitrene groups (═N—CN), cyanate groups (—O—CN), isocyanate groups (—N═C═O), thiocyanate groups (—S—CN), isothiocyanate groups (—N═C═S), nitrosamine groups (═N—N═O), thionitrosamine groups (═N—N═S), nitramine groups (═N—NO2), thionitramine groups (═N—NS2), carbonylnitrene groups (—CO—N), thiocarbonylnitrene groups (—CS—N), sulfenyl halides (—S—X), sulfoxides (═S═O), sulfones (═S[═O]2), sulfinyl groups (—N═S═O), thiosulfinyl groups (—N═S=S), sulfenyl thiocyanato groups (—S—S—CN), sulfenyl cyanato groups (—S—O—CN), sulfodiimine groups (═S[=NH]2), sulfur dihaloimido groups (—N═SX2), sulfur oxide dihaloimido groups (—N═S[═O]X2), aminosulfur oxide trihalide groups (═N—S[═O]X3), sulfonyl azide groups (—S[═O]2N3), sulfonyl thiocyanate groups (—S[═O]2SCN), sulfonyl cyanate groups (—S[═O]2OCN), sulfonyl cyanide groups (—S[═O]2CN), halosulfonate groups (—S[═O]2OX), phosphonyl thiocyanate groups (—P[═O]OHSCN), phosphonyl cyanate groups (—P[═O]OHOCN), phosphonyl cyanide groups (—P[═O]OHCN), or combinations thereof.
38. The pigment of claim 1 further comprising a solubility control agent.
39. The pigment of claim 38 wherein the solubility control agent is a cationic solubility control agent or an anionic solubility control agent.
40. The pigment of claim 39 wherein the solubility control agent is the cationic solubility control agent selected from H+; Li+; Na+; K+; Rb+; Cs+; NH4+; Mg+2; Ca+2; Sr+2; Be+2; Ba+2; Y+3; La+3; Ce+3; Ce+4; Nd+3; Pr+3; Sc+3; Sm+3; Eu+3; Eu+2; Gd+3; Tb+3; Dy+3; Ho+3; Er+3; Tm+3; Yb+3; Lu+3; Ti+4; Zr+4; Ti+3; Hf+4; Nb+5; Ta+5; Nb+4; Ta+4; V+5; V+4; V+3; Mo+6; W+6; Mo+5; W+5; Mo+4; W+4; Cr+3; Mn+2; Mn+3; Mn+4; Fe+2; Fe+3; Co+2; Co+3; Ni+2; Ni+3; Ni+4; Ru+2; Ru+3; Ru+4; Ru+3; Ir+3; Rh+2; Ir+2; Pd+4; Pt+4; Pd+2; Pt+2; Os+4; Cu+; Cu+2; Cu+3: Ag+; Ag+2; Ag+3; Au+; Au+2; Au+3; Zn+2; Cd+2; Hg+; Hg+2; Al+3; Ga+3; Ga+; In+3; In+; Tl+3; Tl+; Ge+4; Ge+2; Sn+4; Sn+2; Pb+4; P+2; Sb+3; Sb+5; As+3; As+5; Bi+3; Bi+5; organic compounds containing at least one N+ site; organic compounds containing at least one phosphonium site; organic compounds containing at least one arsonium site; organic compounds containing at least one stibonium site; organic compounds containing at least one oxonium site; organic compounds containing at least one sulfonium site; organic compounds containing at least one selenonium site; organic compounds containing at least one iodonium site; quaternary ammonium compounds having a formula NR4+, where R is an alkyl, aromatic, or acyclic organic constituent; or combinations thereof.
41. The pigment of claim 40 wherein the cationic solubility control agent is selected from H+; Li+; Na+; K+; Rb+; Cs+; NH4+; Mg+2; Ca+2; Sr+2; Y+3; La+3; Ce+3; Ce+4; Nd+3; Pr+3; Sc+3; Sm+3; Eu+3; Eu+2; Gd+3; Tb+3; Dy+3; Ho+3; Er+3; Tm+3; Yb+3; Lu+3; Ti+4; Zr+4; Ti+3; Zr+4; Ti+3; Hf+4; Nb+5; Ta+5; Nb+4, Ta+4; Mo+6; W+6; Mo+5; W+5; Mo+4; W+4; Mn+2; Mn+3; Mn+4 Fe+2; F+3; Co+2; Co+3; Ru+2; Ru+3; Ru+4; Rh+3; Ir+3; Rh+2; Ir+2; Pd+4; Pt+4; Pd+2; Pt+2; Cu+; Cu+2; Cu+3; Ag+; Ag+2; Ag+3; Au+; Au+3; Au+3+; Zn'2; Al+3; Ga+3; Ga+; In+3; In+; Ge+4; Ge+2; Sn+4; Sn+2; Sb+3; Sb+5; Bi+3; Bi+5; organic compounds containing at least one N+ site; organic compounds containing at least one phosphonium site; organic compounds containing at least one stibonium site; organic compounds containing at least one oxonium site; organic compounds containing at least one sulfonium site; organic compounds containing at least one iodonium site; quaternary ammonium compounds having a formula NR4+, where R is an alkyl, aromatic, or acyclic organic constituent; or combinations thereof.
42. The pigment of claim 39 wherein the solubility control agent is the anionic solubility control agent selected from fluorotitanates, chlorotitanates, fluorozirconates, chlorozirconates, fluoroniobates, chloroniobates, fluorotantalates, chlorotantalates, molybdates, tungstates, permanganates, fluoroinanganates, chloromanganates, fluoroferrates, chloroferrates, fluorocobaltates, chlorocobaltates, fluorozincates, chlorozincates, borates, fluoroborates, fluoroaluminates, chloroaluminates, carbonates, silicates, fluorosilicates, fluorostannates, nitrates, nitrites, azides, cyanamides, phosphates, phosphites, phosphonates, phosphinites, thiophosphates, thiophosphites, thiophosphonates, thiophosphinites, fluorophosphates, fluoroantimonates, chloroantimonates, sulfates, sulfites, sulfonates, thiosulfates, dithionites, dithionates, fluorosulfates, tellurates, fluorides, chlorides, chlorates, perchlorates, bromides, bromates, iodides, iodates, periodates, heteropolyanions, ferricyanides, ferrocyanides, cyanocobaltates, cyanocuprates, cyanomanganates, cyanates, cyanatoferrates, cyanatocobaltates, cyanatocuprates, cyanatomanganates, thiocyanates, thiocyanatoferrates, thiocyanatocobaltates, thiocyanatocuprates, thiocyanatomanganates, cyanamides, cyanamidoferrates, cyanamidocobaltates, cyanamidocuprates, cyanamidomanganates, nitritoferrates, nitritocobaltates, azides, (thio)carboxylates, di(thio)carboxylates, tri(thio)carboxylates, tetra(thio)carboxylates, (thio)phenolates, di(thio)phenolates, tri(thio)phenolates, tetra(thio)phenolates, (thio)phosphonates, di(thio)phosphonates, tri(thio)phosphonates, (thio)phosphonamides, di(thio)phosphonamides, tri(thio)phosphonamides, amino(thio)phosphonates, diamino(thio)phosphonates, triamino(thio)phosphonates, imino(thio)phosphonates, diimino(thio)phosphonates, (thio)sulfonates, di(thio)sulfonates, tri(thio)sulfonates, (thio)sulfonamides, di(thio)sulfonamides, tri(thio)sulfonamides, amino(thio)sulfonates, diamino(thio)sulfonates, triamino(thio)sulfonates, imino(thio)sulfonates, diimino(thio)sulfonates, (thio)borates, di(thio)borates, (thio)boronates, organic silicates, stibonates, cyanides, cyanochromates, cyanonickelates, cyanatochromates, cyanatonickelates, thiocyanatochromates, thiocyanatonickelates, cyanamidochromates, cyanamidonickelates, nitritonickelates, arsonates, diarsonates, triarsonates, organic selenates, diselenates, triselenates, arsenates, arsenites, fluoroarsenates, chloroarsenates, selenates, selenites, fluorothallates, chlorothallates, iodomercury anions, chloromercurates, bromomercurates, osmates, fluoronickelates, chromates, Reinecke's salt, vanadates, or combinations thereof.
43. The pigment of claim 42 wherein the anionic solubility control agent is selected from fluorotitanates, chlorotitanates, fluorozirconates, chlorozirconates, fluoroniobates, chloroniobates, fluorotantalates, chlorotantalates, molybdates, tungstates, permanganates, fluoromanganates, chloromanganates, fluoroferrates, chloroferrates, fluorocobaltates, chlorocobaltates, fluorozincates, chlorozincates, borates, fluoroborates, fluoroaluminates, chloroaluminates, carbonates, silicates, fluorosilicates, fluorostannates, nitrates, nitrites, azides, cyanamides, phosphates, phosphites, phosphonates, phosphinites, thiophosphates, thiophosphites, thiophosphonates, thiophosphinites, fluorophosphates, fluoroantimonates, chloroantimonates, sulfates, sulfites, sulfonates, thiosulfates, dithionites, dithionates, fluorosulfates, tellurates, fluorides, chlorides, chlorates, perchlorates, bromides, bromates, iodides, iodates, periodates, heteropolyanions, ferricyanides, ferrocyanides, cyanocobaltates, cyanocuprates, cyanomanganates, cyanates, cyanatoferrates, cyanatocobaltates, cyanatocuprates, cyanatomanganates, thiocyanates, thiocyanatoferrates, thiocyanatocobaltates, thiocyanatocuprates, thiocyanatomanganates, cyanamides, cyanamidoferrates, cyanamidocobaltates, cyanamidocuprates, cyanamidomanganates, nitritoferrates, nitritocobaltates, azides, (thio)carboxylates, di(thio)carboxylates, tri(thio)carboxylates, tetra(thio)carboxylates, (thio)phenolates, di(thio)phenolates, tri(thio)phenolates, tetra(thio)phenolates, (thio)phosphonates, di(thio)phosphonates, tri(thio)phosphonates, (thio)phosphonamides, di(thio)phosphonamides, tri(thio)phosphonamides, amino(thio)phosphonates, diamino(thio)phosphonates, triamino(thio)phosphonates, imino(thio)phosphonates, diimino(thio)phosphonates, (thio)sulfonates, di(thio)sulfonates, tri(thio)sulfonates, (thio)sulfonamides, di(thio)sulfonamides, tri(thio)sulfonamides, amino(thio)sulfonates, diamino(thio)sulfonates, triamino(thio)sulfonates, imino(thio)sulfonates, diimino(thio)sulfonates, (thio)borates, di(thio)borates, (thio)boronates, organic silicates, stibonates, or combinations thereof.
44. The pigment of claim 1 wherein the manganese/valence stabilizer complex is adsorbed or mixed onto, into, or with an inert medium selected from oxides, hydroxides, phosphates, borates, silicates, carbonates, aluminates, titanates, molybdates, tungstates, oxalates, polymers, or combinations thereof.
45. The pigment of claim 1 wherein the pigment is colored.
46. The pigment of claim 1 wherein the pigment exhibits a color change between manganese oxidation states.
47. The pigment of claim 1 wherein the pigment is light-fast.
48. A method of making a corrosion-inhibiting pigment comprising:
- providing a solvent;
- providing a manganese source in the solvent forming a manganese solution;
- providing a valence stabilizer; and
- combining the manganese source and the valence stabilizer to form a manganese/valence stabilizer complex.
49. The method of claim 48 wherein the manganese source is selected from divalent manganese sources, trivalent manganese sources, tetravalent manganese sources, heptavalent manganese sources, or combinations thereof.
50. The method of claim 48 further comprising oxidizing the manganese source.
51. The method of claim 50 wherein the manganese source is oxidized by adding an oxidizer to the manganese solution.
52. The method of claim 51 wherein the oxidizer is a dissolved solid, a liquid, or a gas.
53. The method of claim 51 wherein the oxidizer is selected from peroxides, superoxides, persulfates, perborates, pernitrates, perphosphates, percarbonates, persilicates, peraluminates, pertitanates, perzirconates, permolybdates, pertungstates, pervanadates, organic peroxyacid derivatives, ozone, hypochlorites, chlorates, perchlorates, nitrates, nitrites, vanadates, iodates, hypobromites, chlorites, bromates, permanganates, periodates, dissolved oxygen, dissolved chlorine, dissolved fluorine, or combinations thereof.
54. The method of claim 50 wherein the manganese source is oxidized by electrolysis.
55. The method of claim 48 wherein the manganese/valence stabilizer complex is formed by a process selected from precipitation, evaporation, salting out with chemicals, freezing, freeze drying, or firing at an elevated temperature.
56. The method of claim 55 wherein the manganese/valence stabilizer complex is formed by precipitation.
57. The method of claim 48 wherein the manganese source is selected from manganese oxide, manganese dioxide, manganomanganic oxide, manganese sesquioxide, manganese hydroxide, manganese carbonate, manganese silicate, manganese borate, manganese sulfide, manganese phosphate, lithiated manganese spinel, manganese oxalate, manganese nitrate, manganese sulfate, manganese perchlorate, manganese chloride, manganese fluoride, manganese bromide, manganese iodide, manganese bromate, manganese chlorate, manganese fluosilicate, manganese fluotitanate, manganese fluozirconate, manganese fluoborate, manganese fluoaluminate, manganese formate, manganese acetate, manganese propionate, manganese butyrate, manganese valerate, manganese benzoate, manganese glycolate, manganese lactate, manganese tartronate, manganese malate, manganese tartrate, manganese citrate, manganese benzenesulfonate, manganese thiocyanate, manganese acetylacetonate, potassium permanganate, sodium permanganate, lithium permanganate, ammonium permanganate, magnesium permanganate, calcium permanganate, strontium permanganate, barium permanganate, zinc permanganate, ferric permanganate, nickel permanganate, copper permanganate, cobalt permanganate, cerium permanganate, lanthanum permanganate, yttrium permanganate, aluminum permanganate, or combinations thereof.
58. The method of claim 48 wherein the solvent comprises water.
59. The method of claim 48 wherein the solvent comprises an organic solvent.
60. The method of claim 59 wherein the organic solvent is methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, benzyl alcohol, glycerol, ethylene glycol, propylene glycol, cresol, cyclohexanol, butyl Carbitol, Cellosolve, methyl Cellosolve, ethyl lactate, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, diethyl ether, isopropyl ether, furan, tetrahydrofuran, dioxane, tetrahydropyran, methyl formate, ethyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, propylene oxide, acetic acid, propionic acid, butyrolactone, ethylene carbonate, propylene carbonate, benzaldehyde, propyl amine, diethyl amine, ethanolamine, aniline, pyridine, acetonitrile, dimethylformamide, propionitrile, nitrobenzene, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, benzene, toluene, xylene, mineral spirits, kerosene, gasoline, carbon tetrachloride, chloroform, methylene chloride, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, Freon 113, Stoddard's solvent, carbon disulfide, dimethyl sulfoxide, hexamethylphosphoric triamide, or combinations thereof.
61. The method of claim 48 wherein the valence stabilizer is an inorganic valence stabilizer or an organic valence stabilizer.
62. The method of claim 48 further comprising providing a solubility control agent.
63. The method of claim 62 wherein the solubility control agent is a cationic solubility control agent or an anionic solubility control agent.
64. The method of claim 63 wherein the solubility control agent is the cationic solubility control agent selected from H+; Li+; Na+; K+; Rb+; Cs+; NH4+; Mg+2; Ca+2; Sr+2; Be+2; Ba+2; Y+3; La+3; Ce+3; Ce+4; Nd+3; Pr+3; Sc+3; Sm+3; Eu+3; Eu+2; Gd+3; Tb+3; Dy+3; Ho+3; Er+3; Tm+3; Yb+3; Lu+3; Ti+4; Zr+4; Ti+3; Hf+4; Nb+5; Ta+5; Nb+4; Ta+4; V+5; V+4; V+3; Mo+6; W+6; Mo+5 W+5; Mo+4; W+4; Cr+3; Mn+2; Mn+3; Mn+4; Fe+2; Fe+3; Co+2; Co+3; Ni+2; Ni+3; Ni+4; Ru+2; Ru+3; R+4; Rh'3; Ir+3; Rh+2; Ir+2; Pd+4; Pt+4; Pd+2; Pt+2; Os+4; Cu+; Cu+2; Cu+3; Ag+; Ag+2; Ag+3; Au+; Au+2; Au+3; Zn+2; Cd+2; Hg+; Hg+2; Al+3; Ga+3; Ga+; In+3; In+; Tl+3; Tl+; Ge+4; Ge+2; Sn+4; Sn+2; Pb+4; Pb+2; Sb+3; Sb+5; As+3; As+5; Bi+3; Bi+5; organic compounds containing at least one N+ site; organic compounds containing at least one phosphonium site; organic compounds containing at least one arsonium site; organic compounds containing at least one stibonium site; organic compounds containing at least one oxonium site; organic compounds containing at least one sulfonium site; organic compounds containing at least one selenonium site; organic compounds containing at least one iodonium site; quaternary ammonium compounds having a formula NR4+, where R is an alkyl, aromatic, or acyclic organic constituent; or combinations thereof.
65. The method of claim 64 wherein the cationic solubility control agent is selected from H+; Li+; Na+; K+; Rb+; Cs+; NH4+; Mg+2; Ca+2; Sr+2; Y+3; La+3; Ce+3; Ce+4; Nd+3; Pr+3; Sc+3; Sm+3; Eu+3; Eu+2; Gd+3; Tb+3; Dy+3; Ho+3; Er+3; Tm+3; Yb+3; Lu+3; Ti+4; Zr+4; Ti+3; Hf+4; Nb+5; Ta+5; Nb+4; Ta+4; Mo+6; W+6; Mo+5; W+5; Mo+4; W+4; Mn+2; Mn+3; Mn+4; Fe+2; Fe+3; Co+2; Co+3; Ru+2; Ru+3; Ru+4; Rh+3; Tl+3; Rh+2; Ir+2; Pd+4; Pt+4; Pd+2; Pt+2; Cu+; Cu+2; Cu+3; Ag+; Ag+2; Ag+3; Au+; Au+2; Au+3; Zn+2; Al+3; Ga+3; Ga+; In+3; In+; Ge+4; Ge+2; Sn+4; Sn+2; Sb+3; Sb+5; Bi+3; Bi+5; organic compounds containing at least one N+ site; organic compounds containing at least one phosphonium site; organic compounds containing at least one stibonium site; organic compounds containing at least one oxonium site; organic compounds containing at least one sulfonium site; organic compounds containing at least one iodonium site; quaternary ammonium compounds having a formula NR4+, where R is an alkyl, aromatic, or acyclic organic constituent; or combinations thereof.
66. The method of claim 63 wherein the solubility control agent is the anionic solubility control agent selected from fluorotitanates, chlorotitanates, fluorozirconates, chlorozirconates, fluoroniobates, chloroniobates, fluorotantalates, chlorotantalates, molybdates, tungstates, permanganates, fluoromanganates, chloromanganates, fluoroferrates, chloroferrates, fluorocobaltates, chlorocobaltates, fluorozincates, chlorozincates, borates, fluoroborates, fluoroaluminates, chloroaluminates, carbonates, silicates, fluorosilicates, fluorostannates, nitrates, nitrites, azides, cyanamides, phosphates, phosphites, phosphonates, phosphinites, thiophosphates, thiophosphites, thiophosphonates, thiophosphinites, fluorophosphates, fluoroantimonates, chloroantimonates, sulfates, sulfites, sulfonates, thiosulfates, dithionites, dithionates, fluorosulfates, tellurates, fluorides, chlorides, chlorates, perchlorates, bromides, bromates, iodides, iodates, periodates, heteropolyanions, ferricyanides, ferrocyanides, cyanocobaltates, cyanocuprates, cyanomanganates, cyanates, cyanatoferrates, cyanatocobaltates, cyanatocuprates, cyanatomanganates, thiocyanates, thiocyanatoferrates, thiocyanatocobaltates, thiocyanatocuprates, thiocyanatomanganates, cyanamides, cyanamidoferrates, cyanamidocobaltates, cyanamidocuprates, cyanamidomanganates, nitritoferrates, nitritocobaltates, azides, (thio)carboxylates, di(thio)carboxylates, tri(thio)carboxylates, tetra(thio)carboxylates, (thio)phenolates, di(thio)phenolates, tri(thio)phenolates, tetra(thio)phenolates, (thio)phosphonates, di(thio)phosphonates, tri(thio)phosphonates, (thio)phosphonamides, di(thio)phosphonamides, tri(thio)phosphonamides, amino(thio)phosphonates, diamino(thio)phosphonates, triamino(thio)phosphonates, imino(thio)phosphonates, diimino(thio)phosphonates, (thio)sulfonates, di(thio)sulfonates, tri(thio)sulfonates, (thio)sulfonamides, di(thio)sulfonamides, tri(thio)sulfonamides, amino(thio)sulfonates, diamino(thio)sulfonates, triamino(thio)sulfonates, imino(thio)sulfonates, diimino(thio)sulfonates, (thio)borates, di(thio)borates, (thio)boronates, organic silicates, stibonates, cyanides, cyanochromates, cyanonickelates, cyanatochromates, cyanatonickelates, thiocyanatochromates, thiocyanatonickelates, cyanamidochromates, cyanamidonickelates, nitritonickelates, arsonates, diarsonates, triarsonates, organic selenates, diselenates, triselenates, arsenates, arsenites, fluoroarsenates, chloroarsenates, selenates, selenites, fluorothallates, chlorothallates, iodomercury anions, chloromercurates, bromomercurates, osmates, fluoronickelates, chromates, Reinecke's salt, vanadates, or combinations thereof.
67. The method of claim 66 wherein the anionic solubility control agent is selected from fluorotitanates, chlorotitanates, fluorozirconates, chlorozirconates, fluoroniobates, chloroniobates, fluorotantalates, chlorotantalates, molybdates, tungstates, permanganates, fluoromanganates, chloromanganates, fluoroferrates, chloroferrates, fluorocobaltates, chlorocobaltates, fluorozincates, chlorozincates, borates, fluoroborates, fluoroaluminates, chloroaluminates, carbonates, silicates, fluorosilicates, fluorostannates, nitrates, nitrites, azides, cyanamides, phosphates, phosphites, phosphonates, phosphinites, thiophosphates, thiophosphites, thiophosphonates, thiophosphinites, fluorophosphates, fluoroantimonates, chloroantimonates, sulfates, sulfites, sulfonates, thiosulfates, dithionites, dithionates, fluorosulfates, tellurates, fluorides, chlorides, chlorates, perchlorates, bromides, bromates, iodides, iodates, periodates, heteropolyanions, ferricyanides, ferrocyanides, cyanocobaltates, cyanocuprates, cyanomanganates, cyanates, cyanatoferrates, cyanatocobaltates, cyanatocuprates, cyanatomanganates, thiocyanates, thiocyanatoferrates, thiocyanatocobaltates, thiocyanatocuprates, thiocyanatomanganates, cyanamides, cyanamidoferrates, cyanamidocobaltates, cyanamidocuprates, cyanamidomanganates, nitritoferrates, nitritocobaltates, azides, (thio)carboxylates, di(thio)carboxylates, tri(thio)carboxylates, tetra(thio)carboxylates, (thio)phenolates, di (thio)phenolates, tri(thio)phenolates, tetra(thio)phenolates, (thio)phosphonates, di(thio)phosphonates, tri(thio)phosphonates, (thio)phosphonamides, di(thio)phosphonami des, tri(thio)phosphonamides, amino(thio)phosphonates, diamino(thio)phosphonates, triamino(thio)phosphonates, imino(thio)phosphonates, diimino(thio)phosphonates, (thio)sulfonates, di(thio)sulfonates, tri(thio)sulfonates, (thio)sulfonamides, di(thio)sulfonamides, tri(thio)sulfonamides, amino(thio)sulfonates, diamino(thio)sulfonates, triamino(thio)sulfonates, imino(thio)sulfonates, diimino(thio)sulfonates, (thio)borates, di(thio)borates, (thio)boronates, organic silicates, stibonates, or combinations thereof.
68. The method of claim 48 wherein the valence stabilizer is provided by adding it to the manganese solution.
69. The method of claim 48 wherein the valence stabilizer is provided as a separate solution.
70. The method of claim 62 wherein the solubility control agent is provided by adding the solubility control agent to the manganese solution.
71. The method of claim 62 whereby the solubility control agent is provided by adding the solubility control agent to a separate solution containing the valence stabilizer.
72. The method of claim 62 wherein the solubility control agent is provided as a separate solution.
73. The method of claim 48 further comprising heating the manganese solution.
74. The method of claim 48 further comprising cooling the manganese solution.
75. The method of claim 48 further comprising adjusting the pH of the manganese solution using a compound selected from acids or bases.
76. The method of claim 48 further comprising adsorbing or mixing the manganese/valence stabilizer complex onto, into, or with an inert medium selected from oxides, hydroxides, phosphates, borates, silicates, carbonates, aluminates, titanates, molybdates, tungstates, oxalates, polymers, or combinations thereof.
77. A method of making a corrosion-inhibiting pigment comprising:
- providing a manganese source;
- providing a valence stabilizer; and
- heating the manganese source and the valence stabilizer in an oxidizing environment to form a pigment containing trivalent or tetravalent manganese.
78. The method of claim 77 wherein the manganese source is selected from divalent manganese sources, trivalent manganese sources, tetravalent manganese sources, heptavalent manganese sources, or combinations thereof.
79. The method of claim 77 wherein the manganese source is selected from manganese oxide, manganese dioxide, manganomanganic oxide, manganese sesquioxide, manganese hydroxide, manganese carbonate, manganese silicate, manganese borate, manganese sulfide, manganese phosphate, lithiated manganese spinel, manganese oxalate, manganese nitrate, manganese sulfate, manganese perchlorate, manganese chloride, manganese fluoride, manganese bromide, manganese iodide, manganese bromate, manganese chlorate, manganese fluosilicate, manganese fluotitanate, manganese fluozirconate, manganese fluoborate, manganese fluoaluminate, manganese formate, manganese acetate, manganese propionate, manganese butyrate, manganese valerate, manganese benzoate, manganese glycolate, manganese lactate, manganese tartronate, manganese malate, manganese tartrate, manganese citrate, manganese benzenesulfonate, manganese thiocyanate, manganese acetylacetonate, potassium penmanganate, sodium permanganate, lithium permanganate, ammonium penmanganate, magnesium permanganate, calcium permanganate, strontium permanganate, barium permanganate, zinc permanganate, ferric permanganate, nickel permanganate, copper penmanganate, cobalt penmanganate, cerium penmanganate, lanthanum permanganate, yttrium penmanganate, aluminum permanganate, or combinations thereof.
80. The method of claim 77 wherein the manganese source is a precipitate or a mineral.
81. The method of claim 80 wherein the manganese mineral is selected from manganosite, pyrochroite, rhodochrosite, rhodonite, tephroite, manganhumite, manganjustite, alabandite, hauerite, reddingite, hureaulite, pyrolusite, hausmannite, manganite, ramsdellite, bixbyite, groutite, feitknechite, akhtenskite, buserite, nsutite, hetaerolite, marokite, hydrohetaerolite, braunite, psilomelane, romanechite, cryptomelane, manjiroite, lithiophorite, chalcophanite, hollandite, neltnerite, woodruffite, birnesite, asbolane, todorokite, vernadite, or combinations thereof.
82. The method of claim 77 wherein the valence stabilizer is oxygen.
83. The method of claim 77 wherein the oxidizing environment is selected from oxygen, air, ozone, nitrogen oxides, sulfur oxides, chlorine, fluorine, or combinations thereof.
84. The method of claim 83 wherein the oxidizing environment is selected from oxygen, air, or combinations thereof.
85. The method of claim 77 wherein the manganese-containing mixture is heated to between about 200° C. and about 1200° C.
86. The method of claim 77 further comprising providing a solubility control agent.
87. The method of claim 86 wherein the solubility control agent is a cationic solubility control agent selected from Li+, Na+, K+, Rb+, Cs+, Be+2, Mg+2, Ca+2, Sr'2, Ba+2, Y+3, La+3, Ce+3, Ce+4, Ti+4, Zr+4, V+5, Nb+5, Ta+5, Mo+6, W+6, Cr+3, Mn+2, Fe+3, Fe+2, Co+2, Co+3, Ni+2, Cu+2, Ag+, Ag+2, Zn+2, Al+3, In+3, Sn+4, Sb+3, Sb+5, Bi+3, Bi+5, or combinations thereof.
88. The method of claim 87 wherein the cationic solubility control agent is selected from Ba+2, Bi+3, Bi+5, or combinations thereof.
89. The method of claim 86 wherein the solubility control agent is provided by adding the solubility control agent to the manganese-containing mixture.
90. The method of claim 77 further comprising mixing the manganese/valence stabilizer complex onto, into, or with an inert medium selected from oxides, hydroxides, phosphates, borates, silicates, carbonates, aluminates, titanates, molybdates, tungstates, oxalates, or combinations thereof.
91. A method for treating a surface for corrosion resistance, comprising:
- providing a substrate to be coated; and
- applying a corrosion-inhibiting pigment comprising manganese, where the manganese is trivalent manganese, tetravalent manganese, or combinations thereof, and a valence stabilizer combined to form a manganese/valence stabilizer complex.
92. The method of claim 91 wherein the substrate is subject to water-based electrochemical corrosion.
93. The method of claim 91 wherein the manganese/valence stabilizer complex has a solubility in water of between about 1×100 and about 1×10−17 moles per liter of manganese at about 25° C. and about 760 Torr.
94. The method of claim 93 wherein the solubility of the manganese/valence stabilizer complex in water is between about 1×10−1 and about 1×104 moles per liter of manganese at about 25° C. and about 760 Torr.
95. The method of claim 93 wherein the solubility of the manganese/valence stabilizer complex in water is between about 1×10−6 and about 1×10−8 moles per liter of manganese at about 25° C. and about 760 Torr.
96. The method of claim 93 wherein the solubility of the manganese/valence stabilizer complex in water is between about 1×10−9 and about 1×1017 moles per liter of manganese at about 25° C. and about 760 Torr.
97. The method of claim 91 wherein there is an electrostatic barrier layer around the manganese/valence stabilizer complex in aqueous solution.
98. The method of claim 91 wherein the manganese/valence stabilizer complex acts as an ion exchange agent towards corrosive ions.
99. The method of claim 91 wherein the manganese/valence stabilizer complex decomposes at a temperature above about 100° C.
100. The method of claim 91 wherein the manganese/valence stabilizer complex melts at a temperature above about 50° C.
101. The method of claim 91 wherein the valence stabilizer is an inorganic valence stabilizer or an organic valence stabilizer.
102. The method of claim 93 wherein the manganese/valence stabilizer complex further comprises a solubility control agent.
103. The method of claim 102 wherein the solubility control agent is a cationic solubility control agent or an anionic solubility control agent.
104. The method of claim 103 wherein the solubility control agent is the cationic solubility control agent selected from H+; Li+; Na+; K+; Rb+; Cs+; NH4+; Mg+2; Ca+2; Sr+2; Be+2; Ba+2; Y+3; La+3; Ce+3; Ce+4; Nd+3; Pr+3; Sc+3; Sm+3; Eu+3; Eu+2; Gd+3; Tb+3; Dy+3; Ho+3; Er+3; Tm+3; Yb+3; Lu+3; Ti+4; Zr+4; Ti+3; Hf+4; Nb+5; Ta+5; Nb+4; Ta+4; V+5; V+4; V+3; Mo+6; W+6; Mo+5; W+5; Mo+4; W+4; Cr+3; Mn+2; Mn+3; Mn+4; Fe+2; Fe+3; Co+2; Co+3; Ni+2; Ni+3; Ni+4; Ru+2; Ru+3; Ru+4; Rh+3; Ir+3; Rh+2; Ir+2; Pd+4; Pt+4; Pd+2; Pt+2; Os+4; Cu+; Cu+2; Cu+3; Ag+; Ag+2; Ag3; Au+; Au+2; Au+3; Zn+2; Cd+2; Hg+; Hg+2; Al+3; Ga+3; Ga+; In+3; In+; Tl+3; Tl+; Ge+4; Ge+2; Sn+4; Sn+2; Pb+4; Pb+2; Sb+3; Sb+5; As+3; As+5; Bi+3; Bi+5; organic compounds containing at least one N+ site; organic compounds containing at least one phosphonium site; organic compounds containing at least one arsonium site; organic compounds containing at least one stibonium site; organic compounds containing at least one oxonium site; organic compounds containing at least one sulfonium site;
- organic compounds containing at least one selenonium site; organic compounds containing at least one iodonium site; quaternary ammonium compounds having a formula NR4+, where R is an alkyl, aromatic, or acyclic organic constituent; or combinations thereof.
105. The method of claim 104 wherein the cationic solubility control agent is selected from H+; Li+; Na+; K+; Rb+; Cs+; NH4+; Mg2; Ca+2; Sr+2; Y+3; La+3; Ce+3 Ce+4; Nd+3; Pr+3; Sc+3; Sm+3; Eu+3; Eu+2; Gd+3; Tb+3; Dy+3; Ho+3; Er+3; Tm+3; Yb+3; Lu+3; Ti+4; Zr+4; Ti+3; Hf+4; Nb+5; Ta+5; Nb+4; Ta+4; Mo+6; W+6; Mo+5; W+5; Mo+4; W+4; Mn+2; Mn+3; Mn+4; Fe+2; Fe+3; Co+2; Co+3; Ru+2; Ru+3; Ru+4; Rh+3; Ir+3; Rh+2; Ir+2; Pd+4; Pt+4; Pd+2; Pt+2; Cu+; Cu+2; Cu+3; Ag+; Ag+2; Ag+3; Au+; Au+2; Au+3; Zn+2; Al+3; Ga+3; Ga+; In+3; In+; Ge+4; Ge+2; Sn+4; Sn+2; Sb+3; Sb+5; Bi+3; Bi+5; organic compounds containing at least one N+ site; organic compounds containing at least one phosphonium site; organic compounds containing at least one stibonium site; organic compounds containing at least one oxonium site; organic compounds containing at least one sulfonium site; organic compounds containing at least one iodonium site; quaternary ammonium compounds having a formula NR4+, where R is an alkyl, aromatic, or acyclic organic constituent; or combinations thereof.
106. The method of claim 103 wherein the solubility control agent is the anionic solubility control agent is selected from fluorotitanates, chlorotitanates, fluorozirconates, chlorozirconates, fluoroniobates, chloroniobates, fluorotantalates, chlorotantalates, molybdates, tungstates, permanganates, fluoromanganates, chloromanganates, fluoroferrates, chloroferrates, fluorocobaltates, chlorocobaltates, fluorozincates, chlorozincates, borates, fluoroborates, fluoroaluminates, chloroaluminates, carbonates, silicates, fluorosilicates, fluorostannates, nitrates, nitrites, azides, cyanamides, phosphates, phosphites, phosphonates, phosphinites, thiophosphates, thiophosphites, thiophosphonates, thiophosphinites, fluorophosphates, fluoroantimonates, chloroantimonates, sulfates, sulfites, sulfonates, thiosulfates, dithionites, dithionates, fluorosulfates, tellurates, fluorides, chlorides, chlorates, perchlorates, bromides, bromates, iodides, iodates, periodates, heteropolyanions, ferricyanides, ferrocyanides, cyanocobaltates, cyanocuprates, cyanomanganates, cyanates, cyanatoferrates, cyanatocobaltates, cyanatocuprates, cyanatomanganates, thiocyanates, thiocyanatoferrates, thiocyanatocobaltates, thiocyanatocuprates, thiocyanatomanganates, cyanamides, cyanamidoferrates, cyanamidocobaltates, cyanamidocuprates, cyanamidomanganates, nitritoferrates, nitritocobaltates, azides, (thio)carboxylates, di(thio)carboxylates, tri(thio)carboxylates, tetra(thio)carboxylates, (thio)phenolates, di(thio)phenolates, tri(thio)phenolates, tetra(thio)phenolates, (thio)phosphonates, di(thio)phosphonates, tri(thio)phosphonates, (thio)phosphonamides, di(thio)phosphonamides, tri(thio)phosphonamides, amino(thio)phosphonates, diamino(thio)phosphonates, triamino(thio)phosphonates, imino(thio)phosphonates, diimino(thio)phosphonates, (thio)sulfonates, di(thio)sulfonates, tri(thio)sulfonates, (thio)sulfonamides, di(thio)sulfonamides, tri(thio)sulfonamides, amino(thio)sulfonates, diamino(thio)sulfonates, triamino(thio)sulfonates, imino(thio)sulfonates, diimino(thio)sulfonates, (thio)borates, di(thio)borates, (thio)boronates, organic silicates, stibonates, cyanides, cyanochromates, cyanonickelates, cyanatochromates, cyanatonickelates, thiocyanatochromates, thiocyanatonickelates, cyanamidochromates, cyanamidonickelates, nitritonickelates, arsonates, diarsonates, triarsonates, organic selenates, diselenates, triselenates, arsenates, arsenites, fluoroarsenates, chloroarsenates, selenates, selenites, fluorothallates, chlorothallates, iodomercury anions, chloromercurates, bromomercurates, osmates, fluoronickelates, chromates, Reinecke's salt, vanadates, or combinations thereof.
107. The method of claim 103 wherein the anionic solubility control agent is selected from fluorotitanates, chlorotitanates, fluorozirconates, chlorozirconates, fluoroniobates, chloroniobates, fluorotantalates, chlorotantalates, molybdates, tungstates, permanganates, fluoromanganates, chloromanganates, fluoroferrates, chloroferrates, fluorocobaltates, chlorocobaltates, fluorozincates, chlorozincates, borates, fluoroborates, fluoroaluminates, chloroaluminates, carbonates, silicates, fluorosilicates, fluorostannates, nitrates, nitrites, azides, cyanamides, phosphates, phosphites, phosphonates, phosphinites, thiophosphates, thiophosphites, thiophosphonates, thiophosphinites, fluorophosphates, fluoroantimonates, chloroantimonates, sulfates, sulfites, sulfonates, thiosulfates, dithionites, dithionates, fluorosulfates, tellurates, fluorides, chlorides, chlorates, perchlorates, bromides, bromates, iodides, iodates, periodates, heteropolyanions, ferricyanides, ferrocyanides, cyanocobaltates, cyanocuprates, cyanomanganates, cyanates, cyanatoferrates, cyanatocobaltates, cyanatocuprates, cyanatomanganates, thiocyanates, thiocyanatoferrates, thiocyanatocobaltates, thiocyanatocuprates, thiocyanatomanganates, cyanamides, cyanamidoferrates, cyanamidocobaltates, cyanamidocuprates, cyanamidomanganates, nitritoferrates, nitritocobaltates, azides, (thio)carboxylates, di(thio)carboxylates, tri(thio)carboxylates, tetra(thio)carboxylates, (thio)phenolates, di(thio)phenolates, tri(thio)phenolates, tetra(thio)phenolates, (thio)phosphonates, di(thio)phosphonates, tri(thio)phosphonates, (thio)phosphonamides, di(thio)phosphonamides, tri(thio)phosphonamides, amino(thio)phosphonates, diamino(thio)phosphonates, triamino(thio)phosphonates, imino(thio)phosphonates, diimino(thio)phosphonates, (thio)sulfonates, di(thio)sulfonates, tri(thio)sulfonates, (thio)sulfonamides, di(thio)sulfonamides, tri(thio)sulfonamides, amino(thio)sulfonates, diamino(thio)sulfonates, triamino(thio)sulfonates, imino(thio)sulfonates, diimino(thio)sulfonates, (thio)borates, di(thio)borates, (thio)boronates, organic silicates, stibonates, or combinations thereof.
108. The method of claim 100 wherein the manganese/valence stabilizer complex is adsorbed onto, into, or mixed with an inert medium selected from oxides, hydroxides, phosphates, borates, silicates, carbonates, aluminates, titanates, molybdates, tungstates, oxalates, polymers, or combinations thereof.
109. The method of claim 91 wherein the pigment is colored.
110. The method of claim 91 wherein the pigment exhibits a color change between manganese oxidation states.
111. The method of claim 91 wherein the pigment is light-fast.
112. The method of claim 91 wherein the substrate is selected from metals, semimetals, semiconductors, composite materials with anisotropic electrical conductivity, or materials in a conductive or dielectric medium.
113. The method of claim 91 further comprising surface treating the substrate before applying the pigment.
114. The method of claim 91 further comprising applying a coating to the substrate before applying the pigment.
115. The method of claim 91 further comprising applying a coating concurrently with applying the pigment.
116. The method of claim 91 further comprising applying a coating to the substrate, the coating selected from organic coatings, inorganic coatings, or combinations thereof.
117. The method of claim 116 wherein the coating is the organic coating selected from alkyd-type primers, acrylic primers, oil-based primers, polyester primers, epoxy primers, conductive primers, organic sol-gels, ketimine coatings, polyvinyl coatings, acrylic thermoplastics, asphaltic and coal tar thermoplastics, polyamide thermoplastics, polyethylene dispersion thermoplastics, fluorocarbon thermoplastics, chlorocarbon thermoplastics, silicone thermosets, polyurethane thermosets, polyester thermosets, epoxy-amine thermosets, epoxy-amide thermosets, epoxy-ester thermosets, epoxy-coal tar thermosets, furane thermosets, phenolic thermosets, butadiene styrene elastomers, chlorinated rubber elastomers, polysulfonated elastomers, neoprene elastomers, or combinations thereof.
118. The method of claim 116 wherein the coating is the inorganic coating selected from low temperature enamels, low temperature glass frits, carbonaceous coatings, zeolites, inorganic sol-gels, or combinations thereof.
119. A corrosion-inhibiting pigment comprising manganese, wherein the manganese is trivalent manganese, tetravalent manganese, or combinations thereof, and a valence stabilizer combined to form a manganese/valence stabilizer complex, wherein the manganese/valence stabilizer complex is sparingly soluble, exhibits low solubility, or is insoluble in water at about 25° C. and about 760 Torr.
120. A method of making a corrosion-inhibiting pigment comprising:
- providing a solvent;
- providing a manganese source in the solvent forming a manganese solution;
- providing a valence stabilizer; and
- combining the manganese source and the valence stabilizer to form a manganese/valence stabilizer complex, wherein the manganese/valence stabilizer complex is sparingly soluble in water at about 25° C. and about 760 Torr.
121. A method of making a corrosion-inhibiting pigment comprising:
- providing a manganese source;
- providing a valence stabilizer; and
- heating the manganese source and the valence stabilizer in an oxidizing environment to form a pigment containing trivalent or tetravalent manganese, wherein the trivalent manganese or tetravalent manganese compound exhibits low solubility or insolubility in water at about 25° C. and about 760 Torr.
122. A method for treating a surface for corrosion resistance, comprising:
- providing a substrate to be coated; and
- applying a manganese-inhibiting pigment comprising manganese, wherein the manganese is trivalent manganese, tetravalent manganese, or combinations thereof, and a valence stabilizer combined to form a manganese/valence stabilizer complex, wherein the manganese/valence stabilizer complex is sparingly soluble in water at about 25° C. and about 760 Torr.
123. A method for treating a surface for corrosion resistance, comprising:
- providing a substrate to be coated; and
- applying a manganese-inhibiting pigment comprising manganese, wherein the manganese is trivalent manganese, tetravalent manganese, or combinations thereof, and oxygen combined to form a manganese compound wherein the manganese/valence stabilizer complex exhibits low solubility or insolubility in water at about 25° C. and about 760 Torr.
Type: Application
Filed: Jan 13, 2003
Publication Date: Jan 22, 2004
Inventors: Jeffrey A. Sturgill (Fairborn, OH), Andrew Wells Phelps (Kettering, OH)
Application Number: 10341435
International Classification: C01G045/00;
