Synthesis of Silaketenimine Anion and Its Coupling with Isocyanide,Journal of the American Chemical Society

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Synthesis of Silaketenimine Anion and Its Coupling with Isocyanide
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2019-12-04 , DOI: 10.1021/jacs.9b11913
Lizhao Zhu ₁ , Jianying Zhang ₁ , Hao Yang ₁ , Chunming Cui ₁

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Herein, we describe the first synthesis of anionic silaketenimines as well as the coupling product with an isocyanide. Treatment of boryl silanorcaradienyllithium [CH2(L)N]2BSiLi (where L = B[N(Ar)CH]2 and Ar = 2,6-iPr2C6H3) with isocyanides afforded novel silaketenimine anions [CH2(R)N]2BSi(Li)=C=NR featuring a Si=C=N allenic structure. X-ray diffraction studies and density functional theory calculations strongly support the presence of an anionic silicon atom and a strong  bond between the silicon and carbon atoms. One of the silaketenimine anions underwent a formal [2 + 2] cycloaddition reaction with a second molecule of isocyanide to give a novel silacyclopropyl anion with a delocal-ized anionic N C Si C N skeleton. These reactions demon-strated that the bonding nature of the boryl lithiosilylene was distinct from that of common silylenes.

中文翻译：

硅酮亚胺阴离子的合成及其与异氰化物的偶联

在此，我们描述了阴离子硅酮亚胺的首次合成以及与异氰化物的偶联产物。用异氰化物处理硼基硅烷或二烯基锂 [CH2(L)N]2BSiLi（其中 L = B[N(Ar)CH]2 和 Ar = 2,6-iPr2C6H3）得到新型硅酮亚胺阴离子 [CH2(R)N]2BSi(Li) )=C=NR 具有 Si=C=N 等联结构。X 射线衍射研究和密度泛函理论计算强烈支持阴离子硅原子的存在以及硅和碳原子之间的强 π 键。其中一个硅酮亚胺阴离子与第二个异氰化物分子发生正式的 [2 + 2] 环加成反应，得到具有离域阴离子 NC Si CN 骨架的新型硅酮亚胺阴离子。这些反应表明硼基锂硫亚硅烷的键合性质不同于普通亚甲硅烷的键合性质。

更新日期：2019-12-04

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