Abstract: A method is provided for synthesizing a polymer in a controlled fashion using a ring-opening metathesis polymerization (ROMP) reaction, wherein polymerization is carried out using a catalytically effective amount of an olefin metathesis catalyst and a bridged bicyclic or polycyclic olefin monomer that contains at least two heteroatoms directly or indirectly linked to each other. Preferred catalysts are Group 8 transition metal complexes, particularly complexes of Ru and Os. Such complexes include the ruthenium bisphosphine complex (PCy3)2(Cl)2Ru?CHPh (1) and the ruthenium carbene complex (IMesH2)(PCy3)(Cl)2Ru?CHPh (2). The invention also provides novel regioregular polymers synthesized using the aforementioned methodology, wherein the polymers may be saturated, unsaturated, protected, and/or telechelic. An exemplary polymer is poly((vinyl alcohol)2-alt-methylene)(MVOH).

Abstract: A method for producing Group 8 (VIII) metallocene or metallocene-like compounds employs a compound that includes a Cp? anion, such as found, together with a counterion, in a cyclopentadienide or cyclopentadienide-like salt. In one embodiment, the method includes reacting a metal salt, a (Cp) compound, such as a substituted or unsubstituted cyclopentadiene or indene, and a ligand (L) to form an intermediate compound and reacting the intermediate compound with a Cp? compound, eg., a cyclopentadienide or cyclopentadienide-like salt, where the metal salt can be is a ruthenium, an osmium or an iron halide or nitrate and L is an electron pair donor. Unsubstituted, mono-substituted as well as symmetrically or asymmetrically di- or multi-substituted metallocenes or metallocene-like compounds can be produced. In another embodiment, unsubstituted or symmetrically substituted metallocenes are formed by reacting MX2(PPh3)m with a Cp? compound, where m=3 or 4.

Abstract: An organometallic compound having a low melting point, excellent vaporization characteristic and low film formation temperature on a substrate, for forming an iridium-containing thin film by the CVD process is provided. The organometallic iridium compound is represented by the following general formula (1) or (2): wherein R1 represents hydrogen or a lower alkyl group; R2 to R7 each represents hydrogen, a halogen, or the like, provided that specific combinations of R1 to R7 are excluded; R8 represents a lower alkyl group; R9 to R12 each represents hydrogen, a halogen, or the like, provided that specific combinations of R8 to R12 are excluded. Iridium-containing thin films are produced by using the compound as a precursor by CVD process.

Abstract: A composition capable of forming a metal ruthenium film and a ruthenium oxide film by a simple application/baking process, a process for forming a metal ruthenium film and a ruthenium oxide film from the composition, a metal ruthenium film and a ruthenium oxide film formed by the process, and electrodes formed of the films. A solution composition comprising a specific ruthenium complex. The coating film of this solution composition is heated in an atmosphere containing no oxygen or an atmosphere containing oxygen to form a metal ruthenium film or a ruthenium oxide film, respectively, and electrodes formed of the films.

Abstract: Disclosed is a process for forming an organometallic cyclometallated iridium compound comprising reacting an iridium halide complex with a silver salt and excess organic cyclometallating ligand in a diol solvent. The process provides better yields and control of desired isomers.

Abstract: The invention relates to new (pre)catalysts of ruthenium complexes of formula 1, wherein L1, X, X?, R1, R2, R3 and n are defined herein. The novel ruthenium complexes of formula 1 are convenient (pre)catalysts for metathesis reactions and can be applied, e.g., for ring-closing metathesis, cross metathesis or ene-ine metathesis reactions. Another aspect of the invention are the novel intermediates of formula 2.

Abstract: A family of novel hetrocyclic-amide type catalyst precursors useful for the polymerization of olefins, such as ethylene, higher alpha-olefins, dienes, and mixtures thereof.

Abstract: 3,3?-Substituted chiral biaryl phosphine and phosphinite ligands and metal complexes based on such chiral ligands useful in asymmetric catalysis are disclosed. The metal complexes are useful as catalysts in asymmetric reactions, such as, hydrogenation, hydride transfer, allylic alkylation, hydrosilylation, hydroboration, hydrovinylation, hydroformylation, olefin metathesis, hydrocarboxylation, isomerization, cyclopropanation, Diels-Alder reaction, Heck reaction, isomerization, Aldol reaction, Michael addition, epoxidation, kinetic resolution and [m+n] cycloaddition. The metal complexes are particularly effective in Ru-catalyzed asymmetric hydrogenation of beta-ketoesters to beta-hydroxyesters and Ru-catalyzed asymmetric hydrogenation of enamides to beta amino acids.

Abstract: A process of making metal nanoparticles comprising the steps of: providing a precursor composition comprising at least one metallic compound and at least one organic compound; wherein the organic compound is selected from the group consisting of an ethynyl compound, a metal-ethynyl complex, and combinations thereof, wherein the precursor composition is a liquid or solid at room temperature; and heating the precursor composition under conditions effective to produce metal nanoparticles. A metal nanoparticle composition comprising metal nanoparticles dispersed homogenously in a matrix selected from the group consisting of ethynyl polymer, crosslinked ethynyl polymer, amorphous carbon, carbon nanotubes, carbon nanoparticles, graphite, and combinations thereof.

Abstract: The present invention provides a process for preparing a metal carbene complex of formula (I): wherein M is a transition metal atom selected from the group consisting of ruthenium, rhodium, iron, cobalt, osmium and iridium; L denotes neutral donor ligands ligated to said metal, such groups being the same or different; X is an anionic ligand; R1 and R2 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted vinyl, a is 2 or 3 and b is 1 or 2, such process comprising reacting a sulfur ylide of the formula Ar2S?CR1R2 or its precursor with an appropriate metal complex comprising a transition metal atom selected from the group consisting of ruthenium, rhodium, iron, cobalt, osmium and iridium, said metal complex being also

Abstract: The invention relates to an ionic compound corresponding to the formula [R1X1(Z1)—Q?—X2(Z2)—R2]m Mm+ in which Mm+ is a cation of valency m, each of the groups Xi is S?Z3, S?Z4, P—R3 or P—R4; Q is N, CR5, CCN or CSO2R5, each of the groups Zi is ?O, ?NC?N, ?C(C?N)2, ?NS (?Z)2R6 or ?C[S(?Z)2R6]2, each of the groups Ri, is Y, YO—, YS—, Y2N— or F, Y represents a monovalent organic radical or alternatively Y is a repeating unit of a polymeric frame. The compounds are useful for producing ion conducting materials or electrolytes, as catalysts and for doping polymers.

Abstract: The present invention provides a method of manufacturing a bis(cyclopentadienyl)ruthenium, comprising the step of synthesizing a bis(cyclopentadienyl)ruthenium by causing cyclopentadiene, ruthenium chloride and zinc powder to react in an alcohol solvent, wherein the synthesis of the bis(cyclopentadienyl)ruthenium comprises the step of mixing the cyclopentadiene and zinc powder in the alcohol solvent and thereafter adding ruthenium chloride portionwise while holding the temperature of the reaction system at from −70° C. to 20° C. A highly pure product can be obtained through purification of subliming bis(cyclopentadienyl)ruthenium having been synthesized in the synthesis step in an atmosphere under reduced pressure.

Abstract: The present invention relates to novel hexacoordinated metathesis catalysts and to methods for making and using the same. The inventive catalysts are of the formula wherein: M is ruthenium or osmium; X and X1 are the same or different and are each independently an anionic ligand; L, L1′ and L2 are the same or different and are each independently a neutral electron donor ligand; and, R and R1 are each independently hydrogen or a substituent selected from the group consisting of C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkylsulfonyl and C1-C20 alkylsulfinyl and silyl.

Abstract: An organometallic compound having a low melting point, excellent vaporization characteristic and low film formation temperature on a substrate, for forming an iridium-containing thin film by the CVD process is provided.

Abstract: This invention relates to liquid cyclopentadienyltrimethylplatinum compounds selected from (isopropylcyclopentadienyl)trimethylplatinum and (tert-butylcyclopentadienyl)trimethylplatinum. This invention also relates to a process for producing a film, coating or powder by decomposing a cyclopentadienyltrimethylplatinum compound precursor selected from (isopropylcyclopentadienyl)trimethylplatinum and (tert-butylcyclopentadienyl)-trimethylplatinum, thereby producing the film, coating or powder. This invention further relates to a one pot method for producing an organometallic compound comprising reacting a metal source compound, an alkylating agent and a cyclopentadienyl compound under reaction conditions sufficient to produce said organometallic compound.

Abstract: A metal compound obtained by a process comprising the step of contacting, in a specific ratio, a compound represented by the formula M1L1r, a compound represented by the formula R1s-1TH, and a compound represented by the formula R24-nJ(OH)n; a catalyst component for addition polymerization comprising the metal compound; a catalyst for addition polymerization using the catalyst component; and a process for producing an addition polymer using the catalyst.

Abstract: Ruthenium and osmium carbene compounds that are stable in the presence of a variety of functional groups and can be used to catalyze olefin metathesis reactions on unstrained cyclic and acyclic olefins are disclosed. Also disclosed are methods of making the carbene compounds. The carbene compounds are of the formula where M is Os or Ru; R1 is hydrogen; R is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl; X and X1 are independently selected from any anionic ligand; and L and L1 are independently selected from any neutral electron donor. The ruthenium and osmium carbene compounds of the present invention may be synthesized using diazo compounds, by neutral electron donor ligand exchange, by cross metathesis, using acetylene, using cumulated olefins, and in a one-pot method using diazo compounds and neutral electron donors.

Abstract: Metal complexes comprising a polycyclic, fused ring ligand or inertly substituted derivative thereof comprising at least: (1) a cyclopentadienyl ring, (2) a 7 membered polyatomic ring, and (3) one or more aromatic ring systems, with the proviso that said 7 membered ring (2), is fused to both the cyclopentadienyl ring (1), and said one or more aromatic ring systems (3), and substituted in at least one ring position with a substituent group resulting in sp2 hybridization on the ring atom bonded thereto; polymerization catalysts; and olefin polymerization processes using the same are disclosed.

Abstract: The invention concerns an improved method for preparing catalysts for hydrosilylation reactions of compounds with ethylene or acetylene unsaturation (for example olefins or acetylene derivatives), in particular but not exclusively those involving polyorganosiloxanes (POS) bearing Si—H units and POS bearing Si-(ethylene or acetylene unsaturation) units. Said preparation corresponds to the following synthesis (I), wherein: A═B=carbon: T1, T2=cyclohexyl, t-butyl or methyl; T3, T4=H; DVTMS=divinyltetramethylsiloxane; t-BuOK=potassium tert-butylate; T.A=room temperature. The invention is characterised in that it consists in carrying out said synthesis in a single step by bringing together salt (III) above, Karstedt (IV) in the presence of a solvent (V) (THF) and a base (VI) (t-BuOK) at room temperature.

Abstract: Compounds and metal complexes comprising a polycyclic, fused ring ligand or inertly substituted derivative thereof having up to 60 atoms other than hydrogen, said ligand comprising at least: (1) a cyclopentadienyl ring, (2) a 6, 7, or 8 membered ring other than a 6-carbon aromatic ring, and (3) an aromatic ring, with the proviso that said 6, 7, or 8 membered ring (2), is fused to both the cyclopentadienyl ring (1), and the aromatic ring (3), polymerization catalysts, a process to prepare the novel compounds and complexes, and olefin polymerization processes using the same are disclosed.

Abstract: The present invention relates to an oxaliplatin active substance for a pharmaceutical composition, wherein its weight content in oxalic acid is not more than 0.08%, and to a process of preparing the active substance.

Abstract: A catalyst for the manufacture of acrylic acid or methacrylic acid by the oxidation of propylene, acrolein, or isobutylene whereby said catalyst is prepared by reducing a palladium salt or palladium metal to palladium with a reducing agent such as propylene in an oxygen-free single or two phase aqueous organic solvent containing as a co-solvent a maximum concentration of a C2-C6 carboxylic acid or C3-C6 ketone.

Abstract: The present invention provides a process for preparing a metal carbene complex of formula (I): wherein M is a transition metal atom selected from the group consisting of ruthenium, rhodium, iron, cobalt, osmium and iridium; L denotes neutral donor ligands ligated to said metal, such groups being the same or different; X is an anionic ligand; R1 and R2 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted vinyl, a is 2 or 3 and b is 1 or 2, such process comprising reacting a sulfur ylide of the formula Ar2S═CR1R2 or its precursor with an appropriate metal complex comprising a transition metal atom selected from the group consisting of ruthenium, rhodium, iron, cobalt, osmium and iridium, said metal complex being

Abstract: Asymmetric, disubstituted metallocene compounds have the general formula CpMCp′ where M is a metal selected from the group consisting of Ru, Os and Fe; Cp is a first substituted cyclopentadienyl or indenyl moiety that includes at least one substituent group D1; Cp′ is a second substituted cyclopentadienyl or indenyl moiety that includes at least one substituent group D1′. D1 is different from D1′.

Abstract: Compositions comprising (±)-2-((dimethylamino)methyl)cyclohexanone, a transition-metal salt, and an organic solvent and methods of preparing (±)-cis-2-((dimethylamino)methyl)-1-(aryl)cyclohexanols, in particular (±)-cis-2-((dimethylamino)methyl)-1-(3-methoxyphenyl)cyclohexanol, are disclosed herein. In one embodiment, the (±)-2-((dimethylamino)methyl)cyclohexanone and transition-metal salt are in the form of a (±)-2-((dimethylamino)methyl)cyclohexanone:transition-metal salt complex. In another embodimemt, aryl is 3-methoxyphenyl.

Abstract: Disclosed are organometallic compounds derived from Groups VIIb, VIII, IX, and X metals useful as precursors for the formation of metal containing powders and for the chemical deposition of the metals on substrates, particularly for the chemical vapor deposition of metal films suitable for the manufacture of electronic devices. Methods for their use are also disclosed.

Abstract: In one aspect, the invention encompasses a semiconductor processing method of forming a metal-comprising layer over a substrate. A substrate is provided within a reaction chamber, and a source of a metal-comprising precursor is provided external to the reaction chamber. The metal-comprising precursor comprises a metal coordinated with at least one Lewis base to form a complex having a stoichiometric ratio of the at least one Lewis base to the metal. An amount of the at least one Lewis base is distributed within the source to an amount that is in excess of the stoichiometric ratio. At least some of the metal-comprising precursor is transported from the source to the reaction chamber. A metal is deposited from the metal-comprising precursor and onto the substrate within the reaction chamber. In another aspect, the invention encompasses a method of storing a metal-comprising material. A metal-comprising material is dispersed within a solution.

Abstract: The present invention is directed to a process for the production of monoalkylin trihalides of the formula RSnX3 wherein R-alkyl or cycloalkyl and X—Cl, Br or I involving a redistribution reaction between tetraorganotins, triorganotin halides or diorganotin halides and tin tetrahalides, said process comprising contacting tetra-(R4Sn), tri-(R3SnX) or diorganotin halides (R2SnX2) with SnX4 to afford said monoorganotin trihalides in the presence of at least one transition metal complex, said complex comprising at least one transition metal M, selected from Group VIII of the periodic Table of elements, at least one monodentate ligand or bidentate ligand, L, L′, or L″, and optionally one or more anions, X, of an organic or inorganic acid, as a catalyst or catalyst precursor.

Abstract: Compounds having the formula: are disclosed. M1 and M2 are the same or different and are transition metal atoms or ions; Z2 and Z3, independently, are the atoms necessary to complete a 3-12 membered heterocyclic ring; Z1 is an alkylene or arylene group; Q1 and Q2 are the same or different and are electron withdrawing groups; L1 and L3, taken together, represent —O—CR13—O—; L2 and L4, taken together, represent —O—CR14—O—; and R13 and R14 are the same or different and are selected from the group consisting of alkyl groups and aryl groups or R13 and R14 represent alkylene or arylene groups that are directly or indirectly bonded to one another. Methods for making such compounds are also disclosed, as are intermediates which can be used in their preparation. Also disclosed are methods for carrying out C—H insertion reactions using bis-transition metal catalysts, such as the above compounds.

Abstract: The present invention relates to novel hexacoordinated metathesis catalysts and to methods for making and using the same. The inventive catalysts are of the formula wherein: M is ruthenium or osmium; X and X1 are the same or different and are each independently an anionic ligand; L, L1′ and L2 are the same or different and are each independently a neutral electron donor ligand, wherein at least one L, L1′ and L2 is an N-heterocyclic carbene ligand; and, R and R1 are each independently hydrogen or a substituent selected from the group consisting of C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkylsulfonyl and C1-C20 alkylsulfinyl.

Abstract: The invention relates to new (pre)catalysts of ruthenium complexes of formula 1, 1

Abstract: The invention concerns olefin polymerization catalyst component comprising an organometallic compound of general formula I wherein: M is a transition metal of groups 3, 4-10, lanthanide or actinide of the periodic table of the elements; each R is independently a structural bridge rigidly connecting two ligands L1, L2 and L3 and is constituted by 1 to 4 chain atoms selected from carbon, silicon, germanium, oxygen, boron; m, n and o are 0 or 1, with the proviso that m+n+o is 2 or 3; L1 is a ligand of the cyclopentadienyl type or is isolobal to cyclopentadienyl, L2 is a ligand of the cyclopentadienyl type or is isolobal to cyclopentadienyl, or a monovalent anionic ligand selected from the group consisting of N, P, B when m+n=2, it is selected from the group consisting of NR1, PR1, BR1, O and S when m+n=1; L3 is a monovalent anionic ligand selected from the group consisting of N, P, B when n+o=2, it is selected from the group consisting of NR1, PR1

Abstract: The present invention relates to a raw material for CVD comprising an organic iridium compound as a main component, said organic iridium compound being tris(2,4-octanedionato)iridium represented by Formula 1. Particularly preferably, the raw material for CVD consists only of the trans isomer of tris(2,4-octanedionato)iridium.

Abstract: Disclosed are organometallic compounds derived from Groups VIIb, VIII, IX, and X metals useful as precursors for the formation of metal containing powders and for the chemical deposition of the metals on substrates, particularly for the chemical vapor deposition of metal films suitable for the manufacture of electronic devices. Methods for their use are also disclosed.

Abstract: Novel polynuclear organometallic complexes useful as catalysts for the reversible deshydrogenation of alkanes and alkane group are disclosed. The novel compounds comprise a first transition, a second transition metal p-bonded to an ?5-aromatic ligand, and a pincer ligand. The pincer ligand comprises a 6p-electron aromatic ring having at least 2 ring atoms in an 1, 3 relationship bonded each to a neutral Lewis base through a bridge, the bridge being a diradical. The pincer ligand binds the first transition metal through each of the Lewis bases and through the ring atom adjacent to both Lewis bases and p-coordinates the second transition metal through all aromatic ring atoms. The first transition metal may also bond to 2 or 4 hydrogen atoms.

Abstract: A process for the preparation of ruthenium compounds of the formula {Ru(dienyl)2} wherein “dienyl” represents a substituted pentadienyl or cycloheptadienyl group by reacting dichloro(2,7-dimethylocta-2,6-dien-1,8-diyl)-ruthenium with an appropriate diene in the presence of a primary or secondary alcohol capable of reducing Ru(IV) to Ru(II); and a carbonate of an alkaline material. These ruthenium compounds are useful as precursors of Ru catalysts.

Abstract: This invention provides raw material compounds for use in CVD which contain organic ruthenium compounds as a main ingredient, the organic ruthenium compounds having two &bgr;-diketones plus one diene, one diamine or two organic ligands which are coordinated with ruthenium. In this invention, the vapor pressures of the organic ruthenium compounds are made preferable by specifying the number of the carbon atoms contained in the above &bgr;-diketones and the types of the above diene etc.

Abstract: A catalytic transfer hydrogenation process is provided. The catalyst employed in the process is a metal hydrocarbyl complex which is coordinated to defined bidentate ligands substituted with at least one group selected from an optionally substituted sulphonated hydrocarbyl group, a sulphonated perhalogenated hydrocarbyl group, or an optionally substituted sulphonated heterocyclyl group. Preferred metals include rhodium, ruthenium and iridium. Preferred bidentate ligands are diamines and aminoalcohols, particularly those comprising chiral centres. The hydrogen donor is advantageously a secondary alcohol or a mixture of triethylamine and formic acid. The process can be employed to transfer hydrogenate ketones and imines, which are preferably prochiral. Catalysts for use in such a process are also provided.

Abstract: The invention relates to a method for producing substituted cyclopentadiene compounds and to cyclopentadiene compounds obtained by said method.

Abstract: Platinum compounds, pharmaceutically acceptable salts, and prodrugs thereof. Compositions that include the platinum compounds, either alone or in combination with at least one additional therapeutic agent, with a pharmaceutically acceptable carrier. Methods for using the platinum compounds, either alone or in combination with at least one additional therapeutic agent, in the prophylaxis or treatment of proliferative diseases.

Abstract: A composite metal polybasic salt containing a trivalent metal and magnesium as metal components and having a novel crystal structure, and a method of preparing the same. The invention further deals with a composite metal polybasic salt which has anion-exchanging property, which by itself is useful as an anion-exchanger, capable of introducing anions suited for the use upon anion-exchange, and finds a wide range of applications, and a method of preparing the same. The composite metal polybasic salt has a particular chemical composition and X-ray diffraction peaks, and further has a degree of orientation (Io) of not smaller than 1.5.

Abstract: The invention comprises a chemical composition with the structure shown below. The composition can be polymerized or pyrolyzed, forming transition metal nanoparticles homogeneously dispersed in a thermoset or carbon composition. The size of the nanoparticles can be controlled by manipulating the number and arrangement of functional groups in the composition and by changing the conditions of the polymerization or pyrolysis. The resulting thermosets and carbon compositions have useful magnetic, electric, mechanical, catalytic and/or optical properties.

Abstract: The invention comprises a chemical composition with the structure shown below. The composition can be polymerized or pyrolyzed, forming transition metal nanoparticles homogeneously dispersed in a thermoset or carbon composition. The size of the nanoparticles can be controlled by manipulating the number and arrangement of functional groups in the composition and by changing the conditions of the polymerization or pyrolysis. The resulting thermosets and carbon compositions have useful magnetic, electric, mechanical, catalytic and/or optical properties.

Abstract: Compounds which may be used in the treatment and/or prevention of cancer have the formula (I): wherein R1 and R2 together with the ring to which they are bound represent a saturated or unsaturated carbocyclic or heterocyclic group.

Abstract: A 3+ metal complex for coordination polymerization of olefins is disclosed. The precursor metal complex is stabilized by a anionic multidentate ligand and at least two monoanionic ligands. The multidentate ligand and the transition metal form a metallocycle having at least five primary atoms, counting any &pgr;-bound cyclopentadienyl group in the metallocycle as two primary atoms. Olefin polymerization is exemplified.

Abstract: The invention relates to a method for separating and recovering rhodium from reaction products of oxosynthesis, especially reaction products containing cobalt. The invention also relates to the reuse of rhodium as a catalyst for hydroformulation and to a catalyst for hydroformulation itself. The inventive method is characterized by the following: extraction of the organic solution with an aqueous phosphate solution or a phosphate solution, water washing, oxidative treatment of the organic phase, and extraction of the organic phase with an aqueous water-soluble arylphosphine solution.

Abstract: Methods and compositions for the generation of polypeptides having varied material properties are disclosed herein. Methods include means for initiating the polymerization of aminoacid-N-carboxyanhydride (NCA) monomer by combining the monomer with an amido-containing metallacycle, for making self assembling amphiphilic block copolypeptides and related protocols for adding oligo(ethyleneglycol) functionalized aminoacid-N-carboxyanhydrides (NCAs) to polyaminoacid chains. Additional methods include means of adding an end group to the carboxy terminus of a polyaminoacid chain by reacting an alloc-protected amino acid amide with a transition metal-donor ligand complex to forming an amido-amidate metallacycle for use in further polymerization reactions. Novel compositions for use in peptide synthesis and design including five and six membered amido-containing metallacycles and block copolypeptides are also disclosed.

Abstract: A complex suitable for the polymerization of l-olefins is disclosed, having the Formula A wherein M is a transition metal, lanthanide or actinide; X represents an atom or group covalently or ionically bonded to the transition metal M; b is the valency of the atom or group X; Z1 is N or P; Z2 is N, P, N−, P−or NR5; Z3 is one of N, P, O, S, NHR3, NR3R4, OH, OR3, SH, SR3, PHR3, PR3R4, (NR3)−, O−, S−, (PR3)−, P(R3R4)O, NR3 or PR3 to the proviso that one of Z2 and Z3 is anionic; T is the oxidation state of the transition metal M when both Z2 or Z3 are neutral, and is one less than the oxidation state of M when one of Z2 or Z3 is anionic; A and B are independently hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, and may together with Z2 form part of a heterocyclic substituent; B may be joined to Z3 by either a single or a double bond; R1 to R5 are each independently selected from hydrogen, halogen, hydrocarbyl, substitute

Abstract: Methods and compositions for the generation of polypeptides having varied material properties are disclosed herein. Methods include means for making block copolypeptides and related protocols for adding aminoacid-N-carboxyanhydrides (NCAs) to polyaminoacid chains by exposing the NCA to solutions containing polyaminoacid chains having an amido amidate metallacyle end groups and reacting the NCA with the amido containing metallacyle end group so that the NCA is added to the polyaminoacid chain. Addition methods include means of controlling the addition of aminoacid-N-carboxyanhydrides to polyaminoacid chains by reacting NCAs with initiator molecules and allowing initiator complexes to open the ring of the NCAs through oxidative addition across either the O—C5 or O—C2 anhydride bond resulting a controlled polypeptide polymerization. Novel compositions for use in peptide synthesis and design including five and six membered amido-containing metallacycles and block copolypeptides are also disclosed.

Abstract: The present invention generally relates to the use of certain ruthenium and osmium complexes that are substantially inactive at a first temperature (preferably about room temperature) but becomes progressively more active at a higher second temperature. This difference in reactivities allows the reaction mixture to be formed and manipulated at the first temperature until polymerization is desired. When appropriate, the reaction mixture is heated to a suitable temperature (preferably greater than 50° C.) to activate the catalyst and to initiate polymerization. Because both the initiation and the rate of polymerization may be controlled with temperature, the inventive methods are especially suitable for ring opening metathesis polymerization (“ROMP”) reactions and for molding polymer articles that require extended pot-lives.