Reduction of carbon dioxide and organic carbonyls by hydrosilanes catalysed by the perrhenate anion

Morris, Danny S. and Weetman, Catherine and Wennmacher, Julian T. C. and Cokoja, Mirza and Drees, Markus and Kühn, Fritz E. and Love, Jason B. (2017) Reduction of carbon dioxide and organic carbonyls by hydrosilanes catalysed by the perrhenate anion. Catalysis Science and Technology, 7 (13). pp. 2838-2845. ISSN 2044-4753

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    Abstract

    The simple perrhenate salt [N(hexyl)4][(ReO4)] acts as a catalyst for the reduction of organic carbonyls and carbon dioxide by primary and secondary hydrosilanes. In the case of CO2, this results in the formation of methanol equivalents via silylformate and silylacetal intermediates. Furthermore, the addition of alkylamines to the reaction mixture favours catalytic amine N-methylation over methanol production under certain conditions. DFT analysis of the mechanism of CO2 reduction shows that the perrhenate anion activates the silylhydride forming a hypervalent silicate transition state such that the CO2 can directly cleave a Si–H bond.