Neutral zero-valent s-block complexes with strong multiple bonding

Merle Arrowsmith, Holger Braunschweig, Mehmet Ali Celik, Theresa Dellermann, Rian D. Dewhurst, William C. Ewing, Kai Hammond, Thomas Kramer, Ivo Krummenacher, Jan Mies, Krzysztof Radacki, Julia K. Schuster

The metals of the s block of the periodic table are well known to be exceptional electron donors, and the vast majority of their molecular complexes therefore contain these metals in their fully oxidized form. Low-valent main-group compounds have recently become desirable synthetic targets owing to their interesting reactivities, sometimes on a par with those of transition-metal complexes. In this work, we used stabilizing cyclic (alkyl)(amino)carbene ligands to isolate and characterize the first neutral compounds that contain a zero-valent s-block metal, beryllium. These brightly coloured complexes display very short beryllium-carbon bond lengths and linear beryllium coordination geometries, indicative of strong multiple Be-C bonding. Structural, spectroscopic and theoretical results show that the complexes adopt a closed-shell singlet configuration with a Be(0) metal centre. The surprising stability of the molecule can be ascribed to an unusually strong three-centre two-electron π bond across the C-Be-C unit.