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s 区多重键:一种铍亚胺配合物的分离

s-Block Multiple Bonds: Isolation of a Beryllium Imido Complex.

作者信息

Wang Guocang, Walley Jacob E, Dickie Diane A, Molino Andrew, Wilson David J D, Gilliard Robert J

机构信息

Department of Chemistry, University of Virginia, 409 McCormick Rd./ PO Box 400319, Charlottesville, VA, 22904, USA.

Department of Chemistry and Physics, La Trobe Institute for Molecular Science, La Trobe University, Melbourne, Australia.

出版信息

Angew Chem Int Ed Engl. 2021 Apr 19;60(17):9407-9411. doi: 10.1002/anie.202016027. Epub 2021 Mar 10.

Abstract

A common feature of d- and p-block elements is that they participate in multiple bonding. In contrast, the synthesis of compounds containing homo- or hetero-nuclear multiple bonds involving s-block elements is extremely rare. Herein, we report the synthesis, molecular structure, and computational analysis of a beryllium imido (Be=N) complex (2), which was prepared via oxidation of a molecular Be precursor (1) with trimethylsilyl azide Me SiN (TMS-N ). Notably, compound 2 features the shortest known Be=N bond (1.464 Å) to date. This represents the first compound with an s-block metal-nitrogen multiple bond. All compounds were characterized experimentally with multi-nuclear NMR spectroscopy ( H, C, Be) and single-crystal X-ray diffraction studies. The bonding situation was analyzed with density functional theory (DFT) calculations, which supports the existence of π-bonding between beryllium and nitrogen.

摘要

d区和p区元素的一个共同特征是它们能形成多重键。相比之下,含有涉及s区元素的同核或异核多重键的化合物的合成极为罕见。在此,我们报道了一种铍亚胺基(Be=N)配合物(2)的合成、分子结构和计算分析,该配合物是通过用叠氮基三甲基硅烷(Me₃SiN₃,TMS-N₃)氧化分子态铍前驱体(1)制备而成的。值得注意的是,化合物2具有迄今为止已知最短的Be=N键(1.464 Å)。这代表了首个含有s区金属 - 氮多重键的化合物。所有化合物均通过多核核磁共振光谱(¹H、¹³C、⁹Be)和单晶X射线衍射研究进行了实验表征。通过密度泛函理论(DFT)计算分析了成键情况,计算结果支持了铍和氮之间π键的存在。

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