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

The simple perrhenate salt [N(hexyl) 4 ][(ReO 4 )] acts as a catalyst for the reduction of organic carbonyls and carbon dioxide by primary and secondary hydrosilanes. In the case of CO 2 , this results in the formation of methanol equivalents via silylformate and silylacetal intermediates. Furthermo...

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Bibliographic Details
Published in:Catalysis science & technology 2017, Vol.7 (13), p.2838-2845
Main Authors: Morris, Danny S., Weetman, Catherine, Wennmacher, Julian T. C., Cokoja, Mirza, Drees, Markus, Kühn, Fritz E., Love, Jason B.
Format: Article
Language:English
Subjects:
Anions
Carbon dioxide
Carbonyls
Catalysis
Catalysts
Methyl alcohol
Reduction
Silicates
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Summary:The simple perrhenate salt [N(hexyl) 4 ][(ReO 4 )] acts as a catalyst for the reduction of organic carbonyls and carbon dioxide by primary and secondary hydrosilanes. In the case of CO 2 , 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 CO 2 reduction shows that the perrhenate anion activates the silylhydride forming a hypervalent silicate transition state such that the CO 2 can directly cleave a Si–H bond.
ISSN:2044-4753
2044-4761
DOI:10.1039/C7CY00772H