Abstract: Alkanes are catalytically oxidized in air or oxygen using iron-substituted polyoxoanions (POAs) of the formula:H.sub.e-z ?(n-C.sub.4 H.sub.9).sub.4 N!.sub.z (XM.sub.11 M'O.sub.39).sup.-eThe M' (e.g., iron(III)/iron(II)) reduction potential of the POAs is affected by selection of the central atom X and the framework metal M, and by the number of tetrabutyl-ammonium groups. Decreased Fe(III)/Fe(II) reduction potential has been found to correlate to increased oxidation activity.

Abstract: Acyclic hydrocarbons having 4 to 7 carbon atoms per molecule are isomerized in the liquid phase by contact with a solid superacid catalyst comprising sulfated oxide or hydroxide of a metal selected from the group consisting of Group III and Group IV metals, to obtain high octane number blending components for motor fuel and/or valuable chemical and fuel intermediates.

Abstract: Hydrocarbons, and particularly lower molecular weight alkanes and cycloalkanes, may readily be oxidized with air or O.sub.2 to form such products as alcohols, ketones, and the like selectively on high yields when there is employed as the catalyst a highly active azide-activated metal coordination complex having the structure ##STR1## where M is a transition metal; " " is a ligand; and X is azide. The invention is also directed to certain novel azide-activated metal coordination complex catalysts per se.

Abstract: A sulfated calcined solid catalyst which comprises (1) oxide or hydroxide of Group III or Group IV, e.g. zirconium, metal, (2) oxide or hydroxide of Group V, Group VI or Group VII, e.g. manganese or molybdenum, metal and (3) oxide or hydroxide of Group VIII, e.g. iron, or cobalt metal, is used to isomerize normal alkanes having 4 to 7 carbon atoms per molecule in the liquid phase to obtain high octane number blending components for motor fuel and/or valuable chemical and fuel intermediates.

Abstract: Polyoxoanions are converted to the corresponding heteropolyacids by conversion to their tetrabutylammonium salt followed by pyrolysis.

Abstract: Hydrocarbons, and particularly lower molecular weight alkanes and cycloalkanes, may readily be oxidized with air or O.sub.2 to form such products as alcohols, ketones, and the like selectively high yields when there is employed as the catalyst a coordination complex containing an iron center and a halogenated ligand having the structure ##STR1## where Fe is iron; " .circle. " is a ligand; X is a halogen substituent of the ligand; and A is an anion.

Abstract: Hydrocarbon, and particularly lower molecular weight alkanes and cycloalkanes, may readily be oxidized with air or O.sub.2 to form such products as alcohols, ketones, and the like in high yields when there is employed as the catalyst a highly active nitride-activated metal coordination complex having the structure ##STR1## where M is a transition metal; " " is a ligand; and X is a nitride. Certain dimeric forms of the above catalyst are also employed herein. It has also been discovered that Group IV through VIII transition metal nitrides are also highly effective oxidation catalysts for lower molecular weight hydrocarbons such as alkanes.

Abstract: Hydrocarbons, and particularly lower molecular weight alkanes and cycloalkanes, may readily be oxidixed with air or O.sub.2 to form such products as alcohols, ketones, and the like selectively in high yields when there is employed as the catalyst a highly active azide-activated metal coordination complex having the structure ##STR1## where M is a transition metal; " " is a ligand; and X is azide. The invention is also directed to certain novel azide-activated metal coordination complex catalysts per se.

Abstract: Alkanes are oxidized in the liquid phase at relatively low temperatures using heteropolyacids or polyoxoanions promoted with azide or certain metals. Such azide catalysts are also part of the invention.

Abstract: Heteropolyacids or polyoxoanions promoted with azide, such as K.sub.6 PW.sub.11 VO.sub.40 N.sub.3, useful in the liquid phase oxidation of alkanes.

Abstract: Ruthenium-cobalt carbonyl catalysts which have been promoted with an organophosphite effectively catalyze the dealkoxyhydroxymethylation of aldehyde acetals to form glycol monoethers. Methylal, for example, may be reacted with syngas, i.e., CO and H.sub.2, in the presence of this phosphite-promoted ruthenium carbonyl cobalt catalyst to form the monomethyl ether of ethylene glycol. In a like manner acetaldehyde may be converted to the corresponding propylene glycol monoether. The process may advantageously be carried out with high yields and selectivities in the presence of a polar or non-polar organic solvent in combination with the catalyst system of this invention.The invention is also directed to certain of the organophosphite-promoted cobalt and ruthenium-cobalt carbonyl catalyst systems per se.

Abstract: The cobalt carbonyl catalyst R.sup.5 CCo.sub.3 (CO).sub.9, desirably with Ru.sub.3 (CO).sub.12, wherein R.sup.5 is hydrogen; alkyl, preferably C.sub.1-5 lower alkyl; cycloalkyl or substituted cycloalkyl; cycloalkenyl, such as cyclohexenyl or cyclooctenyl; C.sub.1-12 alkoxy, such as methoxy or propoxy; aryl or alkyl-, cycloalkyl-, alkoxy-, halo-, or cyano-substituted aryl; cyano; or a silyl carbyne moiety of the formula R.sub.3.sup.6 Si, wherein R.sup.6 is alkyl or aryl, effectively catalyzes the dealkoxyhydroxymethylation of aldehyde acetals to form glycol monoethers. Methylal, for example, may be reacted with syngas; i.e., CO and H.sub.2, in the presence of this catalyst system to form the corresponding ethylene glycol monomethyl ether.The novel catalyst combination of R.sup.5 CCo.sub.3 (CO).sub.9 and Ru.sub.3 (CO).sub.12 is likewise claimed herein.

Abstract: The cobalt carbonyl catalyst R.sup.5 CCo.sub.3 (CO).sub.9, desirably with Ru.sub.3 (CO).sub.12, wherein R.sup.5 is hydrogen; alkyl, preferably C.sub.1-5 lower alkyl; cycloalkyl or substituted cycloalkyl; cycloalkenyl, such as cyclohexenyl or cyclooctenyl; C.sub.1-12 alkoxy, such as methoxy or propoxy; aryl or alkyl-, cycloalkyl-, alkoxy-, halo-, or cyano-substituted aryl; cyano; or a silyl carbyne moiety of the formula R.sub.3.sup.6 Si, wherein R.sup.6 is alkyl or aryl, effectively catalyzes the dealkoxyhydroxymethylation of aldehyde acetals to form glycol monoethers. Methylal, for example, may be reacted with syngas; i.e., CO and H.sub.2, in the presence of this catalyst system to form the corresponding ethylene glycol monomethyl ether.

Abstract: The ruthenium-cobalt carbonyl metal cluster catalyst Co.sub.2 Ru(CO).sub.11 effectively catalyzes the dealkoxyhydroxymethylation of aldehyde acetals to form glycol monoethers. Methylal, for example, may be reacted with syngas, i.e., CO and H.sub.2, in the presence of this ruthenium-cobalt cluster catalyst to form the monomethyl ether of ethylene glycol.

Abstract: Hydrogenolysis of a saturated endo-endo dihydronorbornadiene hexacyclic dimer involves the use of a catalytic amount of a Group VIII metal and the presence of hydrogen. The resulting pentacyclic isomers can be used as a diluent for depressing the freezing point of the saturated hexacyclic dimer which is a component of a high density missile fuel.

Abstract: Norbornadiene [bicyclo (2.2.1) heptadiene-2,5] is dimerized to a mixture of mainly the exo-endo stereoisomer of the hexacylic dimer of norbornadiene at both an excellent selectivity and conversion using an effective amount of a two component catalytic system of rhodium acetylacetonate and diethylaluminum chloride or ethylaluminum dichloride or aluminum ethylsesquichloride. The mixture also contains the endo-endo stereoisomer and some trimer. After hydrogenation a suitable mixture of the exo-endo and endo-endo dimers can be used as a component of high energy fuel.

Abstract: Hydrogenolysis of a saturated endo-endo dihydronorbornadiene hexacyclic dimer involves the use of a catalytic amount of a Group VIII metal and the presence of hydrogen. The resulting pentacyclic isomers can be used as a diluent for depressing the freezing point of the saturated hexacyclic dimer which is a component of a high density missile fuel.

Abstract: The removal of color bodies from an olefinic or saturated endo-endo hexacyclic homodimer of norbornadiene or mixtures thereof is accomplished by the use of a serpentine clay. Also acid bentonite clay or a montmorillonite clay can be used to remove the color bodies from the saturated dimer. The saturated dimer has a high density and a high heat of combustion making it useful as a missile fuel. Removal of the color bodies avoids possible catalyst poisoning in the hydrogenation of the olefinic to the saturated dimer. Also removal of the color bodies from the saturated dimer eliminates the possible problem of a material precipitating out on engine turbine blades and causing maintenance or operational problems.

Abstract: Novel codimer (I) of norbornadiene and 1,3-cyclohexadiene and its hydrogenated derivative (II), having the following structures: ##STR1## and processes for preparing both are disclosed. Product (II) can be used as a high energy fuel. Process for codimer I involves use of three component homogeneous catalytic system of cobaltic or cobaltous acetylacetonate, 1,2-bisdiphenylphosphino ethane and one of three alkyl aluminum chlorides.

Abstract: Isomerization of a liquid, saturated endo-endo norbornadiene hexacyclic dimer involves the use of a catalytic amount of acidic alumina or a montmorillonite. The resulting isomeric product is solid, at ambient temperature, and can be used as a missile fuel.