| 摘要 |
Hydrocarbons containing one or more olefinic or acetylenic bonds are hydrogenated using as catalyst a rhodium complex of formula RhX(R1R11R111Y)3 wherein X is an anion, Y is phosphorus, arsenic or antimony and R1, R11 and R111 are the same or different and are hydrocarbon, substituted hydrocarbon or heterocyclic groups. The process is preferably carried out in an inert solvent. Example 2 describes the hydrogenation of octene-1, octene-2, vinyl cyclohexene, cyclohexene and di-isobutylene to fully saturated products, and of phenyl acetylene to a mixture of styrene and ethyl benzene.ALSO:The invention comprises rhodium complexes of formula Rh(X)R1R11R111Y)3, wherein Y is phosphorus, arsenic or antimony, X is an anionic element or group and R1, R11 and R111 are the same or different and are hydrocarbon, substituted hydrocarbon (such as alkoxyaryl) or heterocyclic groups. They may generally be prepared by reacting a monovalent rhodium complex containing replaceable neutral ligands with YR1R11R111. The monovalent rhodium complex may for example be RhX(Ph3P)-(cyclo-1,5-octadiene) or preferably is a complex of formula (RhXZ2)n in which Z represents a mono-olefine and n is 2; or Z represents an acyclic conjugated di-olefine and n is 1. The particular compounds RhX(Ph3P)3 may also be prepared from the rhodium salt of X, by heating the rhodium salt with at least a four-fold molar excess of triphenyl phosphine in a suitable solvent. X, in the compounds may, for example, be a cyanide, cyanate, carboxylate or SnCl3- group but is suitably a halogen. The examples describe the preparation of RhCl(Ph3P)3, RhBr(Ph3P)3, RhI(Ph3P)3, RhCl(Ph2EtP)3, RhCl[(P-C6H4Cl)3P]3, and RhCl(Ph3A5)3. The compounds (RhXZ2)n above, when Z is a mono-olefine and X is chlorine, may be prepared by reacting RhCl3 in an alcohol solution with the mono-olefine. (RhCl(cyclo-octene)2)2 may be prepared in this way. When Z is an acyclic conjugated diolefine, the compounds may be prepared by digesting [RhCl(cyclooctene)2]2 with the appropriate diolefine. The invention also comprises a hydrogenation process comprising contacting a compound containing one or more olefinic or acetylenic bonds, and hydrogen with a rhodium complex of the invention. Propionitrile is formed in Example 2 by the hydrogenation of acrylonitrile, using as catalyst a compound of the invention. |
