Reduction of carbon dioxide and organic carbonyls by hydrosilanes catalysed by the perrhenate anion
Reduction of carbon dioxide and organic carbonyls by hydrosilanes catalysed by the perrhenate anion
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DOI：
10.1039/c7cy00772h
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发表时间：
2017-07-07
影响因子：
5
通讯作者：
Love, Jason B.
中科院分区：
文献类型：
--
作者：
Morris, Danny S.;Weetman, Catherine;Love, Jason B.
简单的过氧化氢盐[N.hexyl）（4）][（ReO 4）]作为催化剂，用于通过伯和仲氢硅烷还原有机羰基化合物和二氧化碳。在CO2的情况下，这导致通过甲硅烷基甲酸酯和甲硅烷基缩醛中间体形成甲醇等价物。此外，在某些条件下，向反应混合物中加入烷基胺有利于催化胺N-甲基化而不是甲醇生产。对CO2还原机理的DFT分析表明，过氧化氢阴离子激活了硅烷氢化物，形成了高价硅酸盐过渡态，使得CO2可以直接裂解Si-H键。
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.