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

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 Be⁰ precursor (1) with trimethylsilyl azide Me₃ SiN₃ (TMS-N₃ ). 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 (¹ H, ¹³ C, ⁹ 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.

Keywords: beryllium; carbene; metal-ligand multiple bonds; s-block.