- CATALYSIS OF HYDROSILYLATION. VII. CATALYSIS OF HYDROSILYLATION OF C=C BONDS BY RUTHENIUM PHOSPHINE COMPLEXES
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A full account of the catalysis of hydrosilylation of the C=C bond in olefins, their derivatives with functional groups as well as in vinyl-trisubstituted silanes by ruthenium(II) and ruthenium(III) phosphine precursors is given.The ruthenium complexes are far more efficient catalysts for the hydrosilylation of 1-alkenes and vinyl-substituted silanes than for the substituted olefins and unsaturated esters.General features characterizing all hydrosilylation reactions catalyzed by the above catalysts are as follows: the reaction proceeds with alkoxy-substituted silanes(also with vinylsilanes) in the absence of solvent, and is enhanced (for RuII and olefins occurs exclusively) in the presence of molecular oxygen.Two general mechanisms are proposed for hydrosilylation of olefins and of vinylsilanes, respectively, which account for most of the experimental observations.
- Marciniec, Bogdan,Gulinski, Jacek
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- Effect of triarylphosphane ligands on the rhodium-catalyzed hydrosilylation of alkene
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A series of triarylphosphanes (1a, 2a, 3a, 4a, 5a, 6a, 7a, 8a, 9a, 10a, 11a) have been synthesized. An X-ray crystal structure analysis of (2-bromophenyl)diphenylphosphane (1a) unambiguously confirmed the constitution of the functionalized phosphane. The hydrosilylation reaction of styrene with triethoxysilane catalyzed with RhCl3/triarylphosphane was studied. In comparison with the classic Wilkinson's catalyst, rhodium complexes with functionalized triarylphosphane ligands are characterized by a very high catalytic effectiveness for the hydrosilylation of alkene. Among these catalysts tested, RhCl3/diphenyl(2-(trimethylsilyl)phenyl)phosphane (8a) exhibited excellent catalytic properties. Using this silicon-containing phosphane ligand for the rhodium-catalyzed hydrosilylation of styrene, both higher conversion of alkene and higher β-adduct selectivity were obtained than with Wilkinson's catalyst.
- Xue, Mei,Li, Jiayun,Peng, Jiajian,Bai, Ying,Zhang, Guodong,Xiao, Wenjun,Lai, Guoqiao
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p. 120 - 126
(2014/02/14)
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