Abstract
A comprehensive and consistent picture of the catalytic cycle of hydrosilylation of alkenes catalysed by hydrido-bridged diplatinum complexes has been derived by means of electronic structure calculations at the B3LYP and CCSD(T) levels of theory, using the LANL2DZ basis set. All crucial reaction steps of the entire catalytic course have been scrutinized. Two critical steps of the catalytic cycle corresponding to the hydride migration to the acceptor C atom of the coordinated olefin substrate and the reductive elimination of the hydrosilylated product were found to be the rate-determining steps with activation barriers in the range of 14–20 and 20–31 kcal mol-1, respectively. The role of the hydrosilane, the “spectator” phosphane ligand and the olefin substrate on the catalytic activity and regioselectivity of the hydrosilylation process is also discussed. Finally, the catalyzed hydrosilylation processes are predicted to be exothermic in line with the experimental observations.
Published Version
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