中性同芳族二硼二硅环丁烯：合成、结构与反应活性
Neutral Homoaromatic Diboradisilacyclobutene: Synthesis, Structure, and Reactivity.
作者信息
Zhang Yu, Wu Linlin, Wang Hao
机构信息
School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, P. R. China.
Hunan Provincial Key Laboratory of Micro & Nano Materials Interfaces Science, College of Chemistry and Chemical Engineering, Central South University, Changsha, 410083, P. R. China.
出版信息
J Am Chem Soc. 2022 Dec 14;144(49):22446-22450. doi: 10.1021/jacs.2c11204. Epub 2022 Dec 2.
A formally neutral homoaromatic diboradisilacyclobutene was prepared and structurally characterized via the reduction of borylaminobromosilane with potassium graphite, which represents the first neutral boron and silicon mixed analogue of the homocyclopropenylium ion. Single-crystal X-ray analyses revealed a folded four-membered BSi ring (26.2°) and a remarkably short transannular B-Si distance of 2.306(3) Å. DFT calculations showed that two π-electrons delocalize over the BSi moiety. Both structural feature and DFT calculations show the significant 2π-homoaromatic nature of the diboradisilacyclobutene. Furthermore, diboradisilacyclobutene reacted readily with CuCl or HCl to afford the diboradisilacyclobutanes.
通过用石墨钾还原硼氨基溴硅烷制备了一种形式上呈中性的同芳族二硼二硅环丁烯，并对其进行了结构表征，它代表了同环丙烯鎓离子的首个中性硼和硅混合类似物。单晶X射线分析揭示了一个折叠的四元BSi环（26.2°）以及一个显著短的跨环B-Si距离，为2.306(3) Å。密度泛函理论计算表明，两个π电子在BSi部分离域。结构特征和密度泛函理论计算均表明二硼二硅环丁烯具有显著的2π同芳族性质。此外，二硼二硅环丁烯很容易与氯化铜或盐酸反应生成二硼二硅环丁烷。
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