Sarkar Samir Kumar, Chaliha Rinkumoni, Siddiqui Mujahuddin M, Banerjee Samya, Münch Annika, Herbst-Irmer Regine, Stalke Dietmar, Jemmis Eluvathingal D, Roesky Herbert W
Institut für Anorganische Chemie, Universität Göttingen, Tammannstrasse 4, 37077, Göttingen, Germany.
Inorganic and Physical Chemistry Department, Indian Institute of Science, Bangalore, 560012, India.
Angew Chem Int Ed Engl. 2020 Dec 14;59(51):23015-23019. doi: 10.1002/anie.202009638. Epub 2020 Oct 12.
We report the design, synthesis, structure, bonding, and reaction of a neutral 2π aromatic three-membered disilaborirane. The disilaborirane is synthesized by a facile one-pot reductive dehalogenation of amidinato-silylene chloride and dibromoarylborane with potassium graphite. Despite the tetravalent arrangement of atoms around silicon, the three-membered silicon-boron-silicon ring is aromatic, as evidenced by NMR spectroscopy, nucleus independent chemical shift calculations, first-principles electronic structure studies using density functional theory (DFT) and natural bond orbital (NBO) based bonding analysis. Trimethylsilylnitrene, generated in situ, inserts in the Si-Si bond of disilaborirane to obtain a four-membered heterocycle 1-aza-2,3-disila-4-boretidine derivative. Both the heterocycles are fully characterized by X-ray crystallography.
我们报道了一种中性2π芳香族三元二硅硼环烷的设计、合成、结构、键合及反应。该二硅硼环烷是通过用石墨钾对脒基亚硅烯氯和二溴芳基硼烷进行简便的一锅法还原脱卤反应合成的。尽管硅周围原子呈四价排列，但通过核磁共振光谱、核独立化学位移计算、基于密度泛函理论（DFT）的第一性原理电子结构研究以及基于自然键轨道（NBO）的键合分析证明，三元硅-硼-硅环是芳香性的。原位生成的三甲基硅基氮烯插入二硅硼环烷的Si-Si键中，得到一种四元杂环1-氮杂-2,3-二硅-4-硼杂环丁烷衍生物。这两种杂环均通过X射线晶体学进行了全面表征。
