σ-Aromaticity Planar Pentacoordinate Beryllium Atoms

Abstract

Six-valence-electron planar pentacoordinate beryllium (ppBe) is explored herein as a global minimum, which is only constructed by s-block metals in BeM₅⁺ (M = Cu, Ag, Au). The bonding in ppBe can be regarded as the excited-stated Be with a 2p_x¹2p_y¹ electronic configuration, forming electron sharing with doublet M₅⁺ motifs followed by two sets of Be(p_∥) → [M₅⁺] σ donations and one Be(s) ← [M₅⁺] σ back-donation. Thus, the σ aromaticity originating from three delocalized σ orbitals gives rise to the whole stability of the high D_5h-symmetry ppBe and strongly enriches s-block planar hypercoordinate bonding.