Patent GB-1138601-A (GB)
Title: Improvements in catalytic reactions
IPC: C07C5/25
Filed: 1964-12-15
Abstract: 1,138,601. Catalytic hydrogenation, hydroformylation and carbonylation processes and complexes containing phosphorus, arsenic or antimony. G. WILKINSON. 13 Dec., 1965 [15 Dec., 1964 (2); 16 Feb., 1965; 5 Oct., 1965], Nos. 50983/64, 50984/64, 6676/65 and 42138/65. Headings C2C and C2J. [Also in Divisions C1 and C5] Alcohols, aldehydes, carboxylic acids and halogenated hydrocarbons are produced in a hydrogenation, hydroformylation or carbonylation process, an unsaturated organic compound is reacted with hydrogen and/or carbon monoxide in the presence of a liquid medium which contains dissolved therein as catalyst a halogen or pseudo-halogen-containing complex which has been formed from a halide or pseudo halide of a platinum group metal and at least one ligand which is either: (a) an organic isocyanide; or (b) an organic compound having in its molecule an atom of an element of Group V B  or VI B  of the Periodic Table, said atom possessing a lone pair of electrons, including phosphorus tri-isocyanate and phosphorus tri-isothiocyanate; or (c) (when the complex is formed from a rhodium or iridium halide and the said process is one of hydroformylation) a stannous or germanium-II halide. In the hydrogenation process the unsaturated organic compound may contain an olefinic, acetylenic or carbonyl bond and in the hydroformylation or carbonylation process the unsaturated organic compound is an ethylenically- or acetylenically-unsaturated hydrocarbon or substituted hydrocarbon. The process may be carried out between 50‹ and 150‹ C. and at a pressure of 5 to 100 atmospheres and the liquid medium may comprise a solvent or co-solvent for the catalytic complex (e.g. lower alkanols, ethers or aliphatic or aromatic hydrocarbons) or it may be constituted by the unsaturated organic reactant or, as the reaction proceeds, the resulting product. The aldehydes obtained by the above hydroformylation reaction may be hydrogenated to the corresponding primary alcohols using the same or different complex catalyst or the said alcohol may be obtained directly from an olefinic or acetylenic hydrocarbon in a single step involving both hydroformylation and hydrogenation. Preferred ligands of type (b) include tertiary amines, phosphines, arsines and stibines; organic nitriles, sulphoxides, phosphine oxides, dialkyl sulphides and mercaptans. The complex catalyst may be represented by the formula LnM<SP>V</SP>Xy, where each L represents a ligand as defined above, M is the platinum group metal, X represents a halogen atom or a pseudo-halogen group (i.e. CN-, CNO- or CNS-) and V is the valency of the metal, and may be neutral or a positively charged ion and may have a tetragonal, octahedral or S-co-ordinate quasi octahedral structure. Specified catalysts are (Ph 3 P) 3 RhCl 3 , (Ph 3 As) 3 RhCl 3 , (Ph 3 As) 2 PtCl 2 , [(Ph 2 EtP) 6 Ru 2 Cl 3 ]Cl, (Ph 3 P) 3 RhCl, Ru(Ph 3 P) 2 Cl 3 MeOH, [Ru 2 (PhEt 2 P) 6 Cl 3 ]Cl, Ru(Ph 3 P) 3 Cl 3 , Ru(Ph 3 P) 4 Cl 2 , Ru(Ph 2 PCH 2 CH 2 PPh 2 ) 2 Cl 2 , Ru(Ph 3 As) 2 Cl 3 MeOH and (SnCl 2 ) 2 RhCl 2 Rh(SnCl 2 ) 2  wherein Ph represents phenyl, Et represents ethyl and Me represents methyl some of which are new compounds. The invention also comprises as new compounds the rhodium-I compounds of the formula (R 3 Z)Rh<SP>I</SP>X where R 3 Z represents a tertiary phosphine, arsine or stibine and X represents a halogen atom or a pseudo-halogen group. These compounds may be obtained by refluxing an excess of a tertiary phosphine, arsine or stibine with a rhodium trihalide in a solvent, e.g. alcohol, or by using tertiary phosphines, arsines or stibines to displace other ligands from rhodium-I complexes.