Catalytichydrosilylation of olefins with organolanthanides: a DFT study. Part I: Hydrosilylation of propene by SiH4

Abstract

Investigation of the catalytic hydrosilylation of propene by primary silane in the presence of Cp₂SmH has been carried out using DFT calculations. Using SiH₄ as a model, it is shown that a catalytic cycle based on the hydride complex is unlikely. The activation of silane after insertion of propene is not competitive compared to the allylic activation of propene or the silyl formation. An alternative catalytic cycle, based on a silyl complex, is proposed. This alternative pathway accounts for the experimental observation. The allylic activation of propene is shown to be one of the main routes for the catalyst deactivation.