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硅烷与镓和硼三卤化物在还原条件下的反应性导致出现意外产物。

Reactivity of Silylene with Gallium- and Boron Trihalide at Reductive Conditions Resulting in Unforeseen Products.

机构信息

Institut für Anorganische Chemie, Universität Göttingen, Tammannstraße 4, 37077, Göttingen, Germany.

Department of Science & Humanities, MLR Institute of Technology, Hyderabad.

出版信息

Chemistry. 2023 May 22;29(29):e202300310. doi: 10.1002/chem.202300310. Epub 2023 Apr 5.

Abstract

Herein, we report a one-pot reaction of gallium and boron halides with potassium graphite in the presence of benzamidinate stabilized silylene LSi-R, (L=PhC(N Bu) ). The reaction of LSiCl with an equivalent amount of GaI in the presence of KC leads to the direct substitution of one chloride group by gallium diiodide simultaneously additional coordination of silylene resulted in L(Cl)Si→GaI -Si(L)→GaI (1). In compound 1, the structure comprises two differently coordinated gallium atoms where one gallium presents between two silylenes and the other gallium is only coordinated by one silylene. In this Lewis acid-base reaction the oxidation states of the starting materials remain unchanged. The same is valid in the silylene boron adduct formation of L( Bu)Si-BPhCl (2) and L( Bu)Si-BBr (3). This new route provides access to galliumhalosilanes challenging to synthesize by any other method.

摘要

在此,我们报告了一种一锅法反应,即在苯甲脒稳定的硅亚胺 LSi-R(L=PhC(N Bu))存在下,将镓和硼卤化物与碳酸钾反应。LSiCl 与等当量的 GaI 在 KC 的存在下反应,导致一价氯被二碘化镓同时取代,此外硅亚胺的额外配位导致 L(Cl)Si→GaI-Si(L)→GaI(1)。在化合物 1 中,结构包括两个不同配位的镓原子,其中一个镓位于两个硅亚胺之间,另一个镓仅由一个硅亚胺配位。在这个路易斯酸碱反应中,起始材料的氧化态保持不变。在 L(Bu)Si-BPhCl(2)和 L(Bu)Si-BBr(3)的硅亚胺硼加合物的形成中也是如此。这条新路线为通过任何其他方法难以合成的卤化硅镓提供了途径。

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