| 摘要 |
Olefinically or acetylenically unsaturated hydrocarbons ar hydrogenated in the presence of a catalyst of formula ZxIr(Rn.X-R1-X1.Rn)2Y where Z is nothing (x=0), a neutral ligand (x=1) or an anionic ligand (x=2 for a monovalent anion or 1 for a divalent anion), X and X1 represent an element or elements of Group VB or VIB, R is hydrogen or an optionally substituted hydrocarbon group, R1 represents a divalent organic group having a chain of z carbon atoms (where z is 1-4), n is 1 or 2 as required to satisfy the valency requirements of X and X1, and Y is a monovalent anion. Examples are given of the hydrogenation of (a) pent-1-ene and hex-3-yne to a mixture of pentane, pentenes, hexane, hexenes and hexynes; (b) oct-1-ene to octane; (c) hex-1-yne and oct-1-ene to a mixture of hexane, hexenes, hex-1-yne, octane and octenes. The hydrogenation is conveniently carried out in benzene solution at elevated pressure and temperature with the catalyst in the liquid phase. The catalyst may be prepared in situ by adding the appropriate starting materials to the hydrogenation reaction mixture.ALSO:The invention comprises complex iridium compounds of the general formula ZxIr(Rn.X-R1-X1-Rn)2Y where Z is nothing (x=0), a neutral ligand (x=1) or an anionic ligand (x=2 for a monovalent anion or 1 for a divalent anion), X and X1 represent an element or elements of Group VB or VIB, e.g. P, Ar or S, and may be the same or different, R represents hydrogen or an optionally substituted hydrocarbon group, R1 represents a divalent organic group having a chain of z carbon atoms (where z is 1-4), n is 1 or 2 as required to satisfy the valency requirements of X and X1 and Y is a monovalent anion. They are prepared by reacting bidentate ligands of the formula (Rn.X.R1.X.Rn) with an iridium complex of formula Irhyh1, where h is a neutral ligand, y is 3 or 4 and h1 is an anionic ligand. The reaction is generally carried out in the liquid phase under an inert atmosphere. The compounds are useful as catalysts for the hydrogenation of olefinically and acetylenically unsaturated compounds, and may be prepared in situ by adding the appropriate starting materials to the hydrogenation reaction mixture. An example is given of the hydrogenation of allyl chloride to a mixture of 2-chloropropane and 1-chloropropane using Ir(Ph2P.CH2CH2PPh2)Cl2.2H2O as catalyst. Compounds in which Y represents perchlorate or tetraphenylboron groups are prepared by reacting the corresponding compounds in which Y is halogen with sodium perchlorate and sodium tetraphenyl boron respectively. |
