Conversion of olefins using complexes of fe,ru,os,rh or ir with organoaluminums

Claim 2

The process according to claim 1 wherein the compound of the metal is an iron, ruthenium osmium, cobalt, rhodium, or iridium halide, cyanide, thiocyanate, cyanate, thriclorostannate, or organic carboxylate wherein the organic carboxylate has up to about 30 carbon atoms; the number of ligand-forming materials and the number of halide, cyanide, thiocyanate, cyanate, thrichlorostannate, or organic carboxylate groups present in the complex is not greater than the number required for the metal to achieve the closed shell electronic configuration of the next higher atomic number inert gas; when the metal is ruthenium or osmium, the number of NO groups is 0-2; and when the metal is iron, two NO groups are present.

Claim 3

a mixture of compounds of (1), wherein R and X are as defined above, and e is 1, 2 or 3, f is 0, 1 or 2, the sum of e and f being 3.

Claim 4

a mixture of ethylene and one or more acyclic, unsubstituted, internal monoolefins of (1);

Claim 5

a mixture of compounds of (1),

Claim 6

a mixture of one or more ReAiXf or AlX3 compounds with one or more compounds having the formula R1gM1hX , or

Claim 7

acyclic, nonconjugated polyenes having five to about 20 carbon atoms per molecule, containing two to about four double bonds per molecule and having at least one double bond with no branching nearer to it than the 3-position and no quaternary carbon atom nearer to it than the 4-position, and mixtures of such polyenes;

Claim 8

A process according to claim 1 wherein the catalyst forms on admixture of a. a metal complex according to the formula (R3Q1)2M2(NO) (NO2)X wherein M2 is rhodium or iridium, Q1 is phosphorus or arsenic, X is a halogen, and R is an aromatic or saturated aliphatic hydrocarbon radical having 20 carbon atoms including alkoxy and halo derivatives thereof; with b. an aluminum-containing adjuvant selected from the group consisting of

Claim 9

a mixture of one or more ReAlXf or AlX3 compounds with one or more compounds having the formula R1gM1Xh, and

Claim 10

an AlX3 compound wherein each R is an aromatic or saturated aliphatic hydrocarbon radical having up to 20 carbon atoms including alkoxy and halo derivatives thereof, preferably an alkyl radical having up to 10 carbon atoms; each R1 is hydrogen or R; each X is a halogen; each M1 is a metal of Group IA, IIA, IIB, or IIIA; e is 1, 2 or 3, f is 0, 1 or 2, the sum of e and f being 3; g is 1, 2 or 3, h is 0, 1 or 2, the sum of g and h being equal to the valence of M1; wherein said ligand-forming material comprises NO; NOX; R3Q; R2Q-QR2; R2N-R2-NR2; CO; unsubstituted or R5-substituted pyridines; unsubstituted or R5-substituted 2,2''-bipyridines; unsubstituted or R-substituted cyclopentadienyl radical-containing compounds; R-S-R, R5(CN)y, R5(COO radical-containing compound; 1,5-cyclooctadiene; dicyclopentadiene; or norbornadiene, wherein x is halogen, R is an aromatic or saturated aliphatic hydrocarbon radical, including alkoxy and halo-substituted radicals, having up to 20 carbon atoms, R1 is hydrogen or R, R2 is a divalent R radical, R is a divalent saturated or ethylenically unsaturated aliphatic hydrocarbon radical having four to 10 carbon atoms, R4 is hydrogen or a methyl radical; R5 is an aromatic, saturated or ethylenically unsaturated aliphatic radical having up to 30 carbon atoms, Q is phosphorus, arsenic or antimony, and y is an integer from 1 to 2.

Claim 11

The process of claim 1 wherein said nonconjugated feed olefin is an acyclic mono- and polyenes having at least three carbon atoms per molecule including cycloalkyl, cycloalkenyl, and aryl derivatives thereof, cyclic mono- and polyenes having at least quaternary carbon atoms per molecule including alkyl and aryl derivatives thereof, mixtures of the above olefins or mixtures of ethylene and the above olefins.

Claim 12

a mixture of ethylene and one or more acyclic polyenes of (3) which contains at least one internal double bond;

Claim 13

an AlX3 compound wherein each R is an aromatic or saturated aliphatic hydrocarbon radical having up to 20 carbon atoms including alkoxy and halo derivatives thereof, preferably an alkyl radical having up to 10 carbon atoms; each R1 is hydrogen or R; each X is a halogen; each M1 is a metal of Group IA, IIA, IIB, or IIIA; e is 1, 2 or 3, f is 0, 1 or 2, the sum of e and f being 3; g is 1, 2 or 3, h is 0, 1 or 2, the sum of g and h being equal to the valence of M1.

Claim 14

cyclopentene;

Claim 15

The process of claim 3 wherein the catalyst consists essentially of (triphenylphosphine)2Rh(NO) (NO2)Cl and ethylaluminum dichloride.

Claim 16

A process according to claim 1 wherein said nonconjugated feed olefin hydrocarbon is selected from the group consisting of

Claim 17

cyclic and bicyclic monoolefins having seven to about 12 ring carbon atoms; including those substituted with up to three alkyl groups having up to about five carbon atoms each with no branching closer to the double bond than the 3-position and with no quaternary carbon atoms closer to the double bond than the 4-position;

Claim 18

a mixture of one or more monocyclic olefins of (6) with ethylene or with one or more unsubstituted, acyclic monoolefins of (1);

Claim 19

The process of claim 1 wherein the molar ratio of the (b) component of the catalyst to the (a) component of the catalyst is in the range of from about 0.1:1 to about 20:1.

Claim 20

cyclic and bicyclic nonconjugated polyenes having five to about 12 ring carbon atoms including those substituted with up to 3 alkyl groups having up to five carbon atoms each, with at least one of the double bonds having no branching closer than the 3-position and no quaternary carbon atom closer than the 4position;

Claim 21

The process of claim 1 wherein said conditions for said olefin disproportionation reaction include a temperature in the range of about -30* to about 75* C, a pressure sufficient to maintain the liquid phase, a time of contact in the range of about 0.1 to about 100 hours, and a ratio of catalyst composition to olefin feed of about 0.001 to about 100 millimoles of Group VIII metal for each mole of olefin feed.

Claim 22

The process of claim 1 wherein the conversion is accomplished in the presence of an inert diluent in which both of the (a) and (b) components of the catalyst are at least partially soluble.

Claim 23

a mixture of one or more monocyclic polyenes of (8) with one or more acyclic 1-olefins having from two to about 10 carbon atoms with no branching closer to the double bond than the 3-position and no quaternary carbon atom closer to the double bond than the 4-position;

Claim 24

polar group-substituted olefinic compounds of classes (1) through (4) and (6) through (9) containing about five to 20 carbon atoms per molecule in which the polar group is no closer to the double bond than the 5-position, and mixtures with unsubstituted member of (1).

Claim 25

The process of claim 1 wherein the catalyst further includes a solid inorganic or organic support or carrier selected from the group consisting of silica, alumina, silica-alumina, titania, boria, zeolites, ion exchange resins, a solid polymer of 4-vinylpyridine and a solid polymer of vinyl dimethylphosphine.

Claim 26

A process for the conversion of at least one nonconjuGated feed olefin having at least three carbon atoms according to the olefin reaction under conditions suitable for said olefin reaction, wherein the conversion according to the olefin reaction can be visualized as comprising the reaction between two first pairs of carbon atoms, the two carbon atoms of each first pair being connected by an olefinic double bond, to form two new pairs from the carbon atoms of said first pairs, the two carbon atoms of each said new pairs being connected by an olefinic double bond, which process comprising contacting said nonconjugated feed olefin with a catalyst which forms on admixture of a. a complex which forms, under complex forming conditions, a compound of the metal iron or cobalt subgroups of Group VIII with at least one ligand-forming material wherein said complex can be represented by the formula ((L)a(Y)bMcZd)x wherein M is a metal of the iron or cobalt subgroups of Group VIII, namely, iron, ruthenium, osmium, cobalt, rhodium, and iridium; each Z is halogen or CN, SCN, OCN, SnCl3, or an organic acid radical having up to about 30 carbon atoms; each (Y) is NO; each (L) is a ligand represented by R3Q, R2Q-QR2, R2NR1, CO, R2N-R2-NR2, unsubstituted or R5-substituted pyridines, unsubstituted or R -substituted 2,2''-bipyridines, unsubstituted or R-substituted pi -cyclopentadienyl radicals, R-S-R, R5(CN)y, R5(COO, 1,5-cyclooctadiene, dicyclopentadiene, or norbornadiene; a is 0-6, b is 1-2, y is 1-2, c is 1-3, d is 0-6, x is a number which is indicative of the polymeric state of the complex, and wherein the number of (L), (Y) and Z groups present in the complex is not greater than the number required for the metal to achieve the closed shell electronic configuration of the next higher atomic number inert gas; when M is Ru or Os, b is 0-2; when M is Fe, b is 2; R is an aromatic or saturated aliphatic hydrocarbon radical, including alkoxy and halo-substituted radicals, having up to 20 carbon atoms; R1 is hydrogen or R; R2 is a divalent R radical; R3 is a divalent saturated or ethylenically unsaturated aliphatic hydrocarbon radical having from four to 10 carbon atoms; R4 is hydrogen or a methyl radical; R5 is an aromatic, saturated aliphatic, or ethylenically unsaturated aliphatic radical having up to 30 carbon atoms; and Q is phosphorus arsenic, or antimony; said aluminum-containing catalytic adjuvant is selected from the group consisting of

Claim 27

The process of claim 10 wherein the olefin hydrocarbon is pentene-1, hexene-1, or pentene-2.

Claim 28

The process of claim 12 wherein the (a) component is (triphenylphosphine)4(CO)2Ru2(SnCl3)Cl3 and the (b) component is methylaluminum sesquichloride.

Claim 29

ThE process of claim 12 wherein the (a) component is NO complexed with RuCl3, and the (b) component is methylaluminum sesquichloride.

Claim 30

The process of claim 12 wherein the (a) component is NO and triphenylphosphine complexed with RuCl3 and the (b) component is methylaluminum sesquichloride.

Claim 31

The process of claim 12 wherein the (a) component is (NO)2RhCl and the (b) component is methylaluminum sesquichloride.

Claim 32

The process of claim 12 wherein the (a) component is NO and triphenylphosphine complexed with RhCl3 and the (b) component is methylaluminum sesquichloride.

Claim 33

The process of claim 12 wherein the (a) component is (Fe(NO)2Cl)2 and the (b) component is methylaluminum sesquichloride.

Claim 34

The process of claim 12 wherein the (a) component is NO and triphenylphosphine complexed with IrCl3 and the (b) component is methylaluminum sesquichloride.

Claim 35

The process of claim 12 wherein the (a) component uses NO and triphenylphosphine complexed with CoCl2 and the (b) component is methylaluminum sesquichloride.