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由氮杂环卡宾（NHC）稳定的亚锡叶立德催化的CO硅氢加成反应。

CO hydrosilylation catalyzed by an N-heterocyclic carbene (NHC)-stabilized stannyliumylidene.

作者信息

Niu Dechuang, Kostenko Arseni, Kelly John A, Sarkar Debotra, Xu Huihui, Inoue Shigeyoshi

机构信息

TUM School of Natural Sciences, Department of Chemistry, Institute of Silicon Chemistry and Catalysis Research Center, Technische Universität München Lichtenbergstraße 4 85748 Garching bei München Germany

出版信息

Chem Sci. 2025 Jan 22;16(9):4014-4022. doi: 10.1039/d4sc07116f. eCollection 2025 Feb 26.

DOI:10.1039/d4sc07116f
PMID:39906378
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11789673/
Abstract

The di-N-heterocyclic carbene (NHCs) stabilized stannyliumylidene, [TerSn(IMe)][BArF], (Ter = 2,6-MesCH, Mes = 2,4,6-Me-CH, IMe = 1,3,4,5-tetramethylimidazol-2-ylidene, BArF = (3,5-(CF)-CH)B), was isolated from the reaction of (Ter)SnCl with two equivalents of IMe, followed by one equivalent of Na[BArF]. This stannyliumylidene acts as a precatalyst for the homogeneous hydrosilylation of CO. Experimental mechanistic studies and quantum chemical calculations have been conducted to elucidate the catalytically active species and the mechanism for the transformation, revealing the stannyliumylidene [TerSn(COIMe)][BArF], which is formed in the presence of CO, as the catalytically active species.

摘要

二氮杂环卡宾（NHCs）稳定的亚锡叶立德[TerSn(IMe)][BArF]（Ter = 2,6-MesCH，Mes = 2,4,6-Me₂CH，IMe = 1,3,4,5-四甲基咪唑-2-亚基，BArF = (3,5-(CF₃)₂C₆H₃)₄B）是由(Ter)₂SnCl与两当量的IMe反应，再加入一当量的Na[BArF]后分离得到的。这种亚锡叶立德作为CO均相硅氢化反应的预催化剂。已进行了实验机理研究和量子化学计算以阐明催化活性物种和转化机理，结果表明在CO存在下形成的亚锡叶立德[TerSn(COIMe)][BArF]是催化活性物种。

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