New Insights into Hydrosilylation of Unsaturated Carbon–Heteroatom (CO, CN) Bonds by Rhenium(V)–Dioxo Complexes

Abstract

The hydrosilylation of unsaturated carbon–heteroatom (CO, CN) bonds catalyzed by high-valent rhenium­(V)–dioxo complex ReO₂I­(PPh₃)₂ (<b>1</b>) were studied computationally to determine the underlying mechanism. Our calculations revealed that the ionic outer-sphere pathway in which the organic substrate attacks the Si center in an η¹-silane rhenium adduct to prompt the heterolytic cleavage of the Si–H bond is the most energetically favorable process for rhenium­(V)–dioxo complex <b>1</b> catalyzed hydrosilylation of imines. The activation energy of the turnover-limiting step was calculated to be 22.8 kcal/mol with phenylmethanimine. This value is energetically more favorable than the [2 + 2] addition pathway by as much as 10.0 kcal/mol. Moreover, the ionic outer-sphere pathway competes with the [2 + 2] addition mechanism for rhenium­(V)–dioxo complex <b>1</b> catalyzing the hydrosilylation of carbonyl compounds. Furthermore, the electron-donating group on the organic substrates would induce a better activity favoring the ionic outer-sphere mechanistic pathway. These findings highlight the unique features of high-valent transition-metal complexes as Lewis acids in activating the Si–H bond and catalyzing the reduction reactions