Claims
- 1. A catalyst for the disproportionation of olefins comprising:
- (1) at least one inorganic metal compound component selected from a chloride or bromide of a metal of Group IVa (including germanium), IVb, Vb, VIb, VIIb, VIII, or Ib of the Periodic Table, or an oxychloride or oxybromide of molybdenum, tungsten, vanadium, or chromium; wherein if the metal is vanadium it is in an oxidation state of either 4 or its highest stable common ionic oxidation state, if the metal is molybdenum, tungsten, or rhenium, it is in an oxidation state of either 5 or its highest stable common ionic oxidation state, and if the metal is other than vanadium, molybdenum, tungsten, or rhenium, the metal is in its highest stable common ionic oxidation state; and
- (2) at least one neutral carbene complex having the general formula ##STR54## wherein R is an alkyl or cycloalkyl radical containing 1 to 10 carbon atoms, an aryl or substituted aryl radical containing 6 to 30 atoms, wherein the substituted radicals have one or more substituents each of which is the same or different and is a halide, alkoxide, or alkyl radical containing 1 to 20carbon atoms; R.sup.I is an alkyl, cycloalkyl, aryl, substituted aryl, triarylsilyl or trialkylsilyl radical containing 1 to 30 carbon atoms, and the aryl substituents are as described for R; M is tungsten or rhenium when component (1) does not contain titanium or M is chromium when component (1) does contain titanium; Y is oxygen, sulfur, selenium, nitrogen or phosphorus; each L is a neutral ligand individually selected from CO, NO, PR.sup.I.sub.3, PCl.sub.3, PF.sub.3, and pyridine, where R.sup.I is as defined above; L.sup.I is cyclopentadienyl; p is 0 or 1; n is 5 when p is 0 and n is 2 when p is 1; and m is 2 when Y is nitrogen or phosphorus and m is 1 when Y is oxygen, sulfur or selenium; wherein the molar ratio of component (1) to component (2) is in the range of 1:1 to 500:1.
- 2. A catalyst according to claim 1, wherein component (1) is at least one metal compound selected from germanium tetrachloride, tin tetrachloride, tin tetrabromide, lead tetrachloride, zirconium tetrachloride, hafnium tetrachloride, vanadium tetrachloride, vanadium oxytrichloride, niobium pentachloride, tantalum pentachloride, chromium trichloride, molybdenum pentachloride, molybdenum pentabromide, molybdenum oxytetrachloride, tungsten hexachloride, tungsten pentabromide, tungsten oxytetrachloride, manganese trichloride, rhenium pentachloride, iron trichloride, iron tribromide, cobalt trichloride, nickel(II) bromide, ruthenium trichloride, rhodium trichloride, palladium dichloride, osmium trichloride, iridium tetrachloride, platinum tetrachloride, copper(II) chloride, copper(II) bromide, silver chloride, and gold(III) chloride.
- 3. A catalyst according to claim 2 wherein said carbene complex component is selected from the group consisting of (methoxyphenylcarbene)pentacarbonyltungsten(0), (p-chlorophenylmethoxycarbene)pentacarbonyltungsten(0), (p-methylphenylmethoxycarbene)pentacarbonyltungsten(0), (p-methoxyphenylmethoxycarbene)pentacarbonyltungsten(0), (phenoxyphenylcarbene)pentacarbonyltungsten(0), (cyclohexyloxyphenylcarbene)pentacarbonyltungsten(0), (butoxyphenylcarbene)pentacarbonyltungsten(0), (octyloxyphenylcarbene)pentacarbonyltungsten(0), (hexadecyloxyphenylcarbene)pentacarbonyltungsten(0), (eicosyloxyphenylcarbene)pentacarbonyltungsten(0), (phenyltrimethylsilyloxycarbene)pentacarbonyltungsten(0), (phenyltriphenylsilyloxycarbene)pentacarbonyltungsten(0), (methylthiophenylcarbene)pentacarbonyltungsten(0), (dimethylaminophenylcarbene)pentacarbonyltungsten(0), (methoxyphenylcarbene)pentanitrosyltungsten(0), (methoxyphenylcarbene).eta..sup.5 -cyclopentadienyldicarbonyl rhenium(I), (methoxyphenylcarbene)tetracarbonyl(triphenylphosphine)tungsten(0), and (methoxyphenylcarbene)pentacarbonylchromium(0).
- 4. A catalyst according to claim 3 wherein said metal compound component is selected from the group consisting of tin tetrachloride, tin tetrabromide, germanium tetrachloride, germanium tetrabromide, lead tetrachloride, and lead tetrabromide and wherein said catalyst composition includes a promoting amount of silicon tetrachloride or silicon tetrabromide.
- 5. A catalyst according to claim 3 wherein said metal compound component is selected from the group consisting of tin tetrachloride, tin tetrabrmode, zirconium tetrabromide, tungsten hexachloride, tungsten hexabromide, tungsten pentachloride, tungsten oxytetrabromide, tungsten oxytetrachloride, and tungsten pentabromide and wherein said catalyst composition includes a promoting amount of at least one tetraorganogermanium compound of the formula GeR.sup.II.sub.4 wherein R.sup.II is an alkyl, aryl, or alkaryl radical containing from 1 to 10 carbon atoms per radical.
- 6. A catalyst according to claim 3 wherein said metal compound component is selected from the tetrachlorides and tetrabromides of germanium, tin, and lead and wherein said catalyst composition includes a promoting amount of carbon tetrachloride.
- 7. A catalyst according to claim 3 wherein said metal compound component is selected from the group of zirconium tetrachloride and zirconium tetrabromide and wherein said catalyst composition further includes a promoting amount of at least one tetraorganotin compound of the formula SnR.sup.II.sub.4 wherein R.sup.II is an alkyl, aryl, or alkaryl radical containing from 1 to 10 carbon atoms per radical.
- 8. A catalyst for the disproportionation of olefins comprising effective amounts of
- (1) silicon tetrachloride,
- (2) at least one neutral carbene complex having the general formula ##STR55## wherein R is selected from the group consisting of alkyl or cycloalkyl radicals containing 1 to 10 carbon per radical and aryl or substituted aryl radicals containing 6 to 30 carbon atoms per radical wherein the substituted radicals can have one or more substitutents each of which can be the same or different and selected from the group consisting of halides, alkoxides, and alkyl radicals containing 1 to 20 carbon atoms per radical; wherein R.sup.I is selected from the group consisting of alkyl, cycloalkyl; aryl, substituted aryl, triarylsilyl, and trialkylsilyl radicals containing 1 to 30 carbon atoms per radical and wherein the aryl substituents are as described for R, Y is O or S, L is CO or NO, and R and R arenot both aryl or substituted aryl when Y is S and nonfunctional olefin reactant is employed; and
- (3) a promoting amount of carbon tetrachloride, wherein the molar ratio of said silicon tetrachloride to said carbene complex component is in the range of about 1/1 to about 500/1 and the molar ratio of said carbon tetrachloride to said silicon tetrachloride is in the range of about 0.1/1 to about 200/1.
- 9. A catalyst according to claim 8 wherein L is CO.
- 10. A catalyst according to claim 9 wherein said carbene complex is (methoxyphenylcarbene)pentacarbonyltungsten(0).
Parent Case Info
This application is a divisional of copending application Ser. No. 101,031, filed Dec. 6, 1979, now U.S. Pat. No. 4,269,780.
US Referenced Citations (10)
Foreign Referenced Citations (1)
Number |
Date |
Country |
773544 |
Apr 1972 |
BEX |
Non-Patent Literature Citations (4)
Entry |
Y. Chauvin et al., "Proceedings of Metathesis Symposium", (1976), pp. 116-124. |
Chem. Absts. 86: 71636y, (1977). |
Chem. Absts. 82: 124822g, (1975). |
Chem. Absts. 85: 178044k, (1976). |
Divisions (1)
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Number |
Date |
Country |
Parent |
101031 |
Dec 1979 |
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