Abstract
Silyloxy-rhodium(I) complexes of the general formula [{(diene)Rh(μ-OSiMe 3)} 2] ( I) where diene=cod, nbd, showed much higher catalytic activity in the hydrosilylation of 1-hexene by triethoxysilane than respective chloro-rhodium(I) complexes, [{(diene)Rh(μ-Cl)} 2] ( II). Kinetic dependence of the rate on the initial concentration of [Rh] and stoichiometric reactions of Rh-complexes with triethoxysilane and 1-hexene allow a distinction between the catalytic cycles of the reactions occurring in the presence of silyloxy-rhodium vs. chloro-rhodium complexes. Direct reaction of triethoxysilane with ( I) was followed by next elementary steps, in particular reductive elimination of disiloxane (EtO) 3SiOSiMe 3 which generates hydridorhodium(I) complex suggested as an intermediate for the catalysis of the hydrosilylation by silyloxy-rhodium complexes.
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