Wang Guocang, Walley Jacob E, Dickie Diane A, Molino Andrew, Wilson David J D, Gilliard Robert J
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.
Angew Chem Int Ed Engl. 2021 Apr 19;60(17):9407-9411. doi: 10.1002/anie.202016027. Epub 2021 Mar 10.
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.
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。