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一种可分离的硼硅烯-氯化物加合物的钾盐。

An Isolable Potassium Salt of a Borasilene-Chloride Adduct.

机构信息

Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai, 980-8578, Japan.

Isobe Degenerate π-Integration Project, Exploratory Research for Advanced Technology (ERATO), Japan Science and Technology Agency, Aoba-ku, Sendai, 980-8577, Japan.

出版信息

Angew Chem Int Ed Engl. 2017 Apr 10;56(16):4593-4597. doi: 10.1002/anie.201612545. Epub 2017 Mar 22.

Abstract

Among the variety of isolable compounds with multiple bonds involving silicon, examples of compounds that contain silicon-boron double bonds (borasilenes) still remain relatively rare. Herein, we report the synthesis of the potassium salt of a chloride adduct of borasilene 1 ([2] ), which was obtained as an orange crystalline solid. Single-crystal X-ray diffraction analysis and reactivity studies on [2] confirmed the double-bond character of the Si=B bond as well as the reduced Lewis acidity, which is due to the coordination of Cl to the boron center. A thermal reaction of [2] afforded a bicyclic product by formal intramolecular C-H insertion across the Si=B bond of 1, which was corroborated by a theoretical study.

摘要

在各种可分离的含硅多重键化合物中,含有硅-硼双键的化合物(硼硅烯)的例子仍然相对较少。在此,我们报告了硼硅烯 1([2])的氯化物加合物的钾盐([2])的合成,该盐以橙色晶体固体形式获得。单晶 X 射线衍射分析和对[2]的反应性研究证实了 Si=B 键的双键性质以及路易斯酸度降低,这是由于 Cl 与硼中心的配位所致。[2]的热反应通过在 Si=B 键上进行的分子内 C-H 插入反应得到了双环产物,这通过理论研究得到了证实。

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