Westfälische Wilhelms-Universität Münster, Institut für Anorganische und Analytische Chemie, Corrensstrasse 28/30, 48149, Münster, Deutschland.
Westfälische Wilhelms-Universität Münster, Organisch Chemisches Institut und Center for Multiscale Theory and Computation, Corrensstrasse 40, 48149, Münster, Deutschland.
Angew Chem Int Ed Engl. 2017 Oct 23;56(44):13866-13871. doi: 10.1002/anie.201705787. Epub 2017 Sep 27.
The reduction of the tribromoamidosilane {N(SiMe )Dipp}SiBr (Dipp=2,6-iPr C H ) with potassium graphite or magnesium resulted in the formation of [Si {N(SiMe )Dipp} ] (1), a bicyclo[1.1.0]tetrasilatetraamide. The Si motif in 1 does not adopt a tetrahedral substructure and exhibits two three-coordinate and two four-coordinate silicon atoms. The electronic situation on the three-coordinate silicon atoms is rationalized with positive and negative polarization based on EPR analysis, magnetization measurements, and DFT calculations as well as Si CP MAS NMR and multinuclear NMR spectroscopy in solution. Reactivity studies with 1 and radical scavengers confirmed the partial charge separation. Compound 1 reacts with sulfur to give a novel type of silicon sulfur cage compound substituted with an amido ligand, [Si S {N(SiMe )Dipp} ] (2).
三溴代酰胺基硅烷{N(SiMe )Dipp}SiBr（Dipp=2,6-iPr C H ）与钾石墨或镁反应，生成[Si {N(SiMe )Dipp} ]（1），一种双环[1.1.0]四硅四酰胺。1 中的 Si 原子团不采用四面体亚结构，而是表现出两个三配位和两个四配位的硅原子。基于 EPR 分析、磁化率测量、DFT 计算以及 Si CP MAS NMR 和多核 NMR 光谱在溶液中的研究，对三配位硅原子上的电子情况进行了正、负极化的合理化。与 1 和自由基清除剂的反应研究证实了部分电荷分离。化合物 1 与硫反应，生成了一种新型的硅硫笼化合物，取代了一个酰胺配体，[Si S {N(SiMe )Dipp} ]（2）。
