Rapid and Mild Synthesis of an NHC-Coordinated Bis(trimethylsilyl)silylene via Elimination of Halotrimethylsilane,Organometallics

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Rapid and Mild Synthesis of an NHC-Coordinated Bis(trimethylsilyl)silylene via Elimination of Halotrimethylsilane
Organometallics ( IF 2.5 ) Pub Date : 2021-07-29 , DOI: 10.1021/acs.organomet.1c00380
Hayato Sasaki ₁ , Yuki Yokouchi ₁ , Takumi Nukazawa ₁ , Takeaki Iwamoto ₁

Affiliation

Base-coordinated silylenes are often used as electron-donating ligands for metal complexes and low-coordinate species of main group elements. However, the synthesis routes to base-coordinated silylenes remain limited. Herein, we report a rapid and mild reaction providing NHC-coordinated bis(trimethylsilyl)silylene 2, which includes the coordination of 1,3,4,5-tetramethylimidazol-2-ylidene (IMe₄) to (Me₃Si)₃SiX (1, X= Cl, Br, and I) and the subsequent elimination of the corresponding Me₃SiX assisted by another IMe₄ molecule. Silylene 2 undergoes not only the coordination to BPh₃ and the addition reactions with 2,3-dimethylbutadiene and Me₃SiI but also an unprecedented substitution reaction with (Me₃Si)₃SiI affording (Me₃Si)₃Si-substituted IMe₄-coordinated silylene 6.

中文翻译：

通过消除卤代三甲基硅烷快速温和地合成 NHC 配位的双（三甲基甲硅烷基）亚甲硅烷

碱配位亚甲硅烷通常用作金属配合物和主族元素的低配位物质的给电子配体。然而，碱配位甲硅烷的合成路线仍然有限。在此，我们报告了一种快速温和的反应，提供了 NHC 配位的双（三甲基甲硅烷基）亚甲硅烷2，其中包括 1,3,4,5-四甲基咪唑-2-亚基（IMe ₄）与（Me ₃ Si）₃ SiX 的配位( 1 , X= Cl, Br, and I) 以及随后在另一个 IMe ₄分子的协助下消除相应的 Me ₃ SiX 。亚甲硅烷2不仅与 BPh _{3 配位}以及与 2,3-二甲基丁二烯和 Me ₃ SiI的加成反应以及与 (Me ₃ Si) ₃ SiI的前所未有的取代反应，提供了 (Me ₃ Si) ₃ Si 取代的 IMe _{4 -}配位亚甲硅烷基6。

更新日期：2021-08-09

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