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Catalysis of hydrosilylation XIII. Gas‐phase hydrosilylation of acetylene by trichlorosilane on functionalised silica supported rhodium and ruthenium phosphine complexes
Author(s) -
Marciniec Bogdan,
Foltynowicz Ze,
Urbaniak WŁOdzimierz,
Perkowski Juliusz
Publication year - 1987
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.590010309
Subject(s) - hydrosilylation , trichlorosilane , chemistry , phosphine , acetylene , ruthenium , catalysis , rhodium , polymer chemistry , organic chemistry , photochemistry , silicon
Gas‐phase hydrosilylation of acetylene by tri‐chlorosilane catalyzed in a continuous flow apparatus by rhodium and ruthenium phosphine complexes immobilized on the silica via mercapto, phosphine, amine and nitrile ligands has been studied. GLC analysis of the reaction products showed vinyltrichlorosilane to be accompanied by products of double hydrosilylation of acetylene and the redistribution of trichlorosilane followed by the hydrosilylation and hydrogenative hydrosilylation of acetylene with dichlorosilane. A scheme for this complex competitive–consecutive reaction was proposed. The yield and selectivity of vinyltrichlorosilane can be much improved under special reaction conditions, e.g. rate flow of the particular substrates, temperature, given catalyst and others. Kinetic measurements carried out in the range of 115–140°C allowed us to evaluate the activation energy, E a , for the vinyltrichlorosilane synthesis, which varied between 20.5 and 27.6 kJ mol −1 for the selected rhodium and ruthenium supported complexes.