Be4 B12 + : A Covalently Bonded Archimedean Beryllo-Borospherene

Angew Chem Int Ed Engl. 2022 Oct 17;61(42):e202208152. doi: 10.1002/anie.202208152. Epub 2022 Sep 16.


A new class of beryllium-boron clusters, beryllo-borospherene, is described herein theoretically. When beryllium is gradually added to the B12 motif, it undergoes drastic structural modifications. The global minimum of the Be4 B12 + cluster is an Archimedean beryllo-borospherene in a 2 A1 electronic ground state, composed of four boron triangles linked at each corner, resulting in a truncated tetrahedron with four B6 rings capped with four beryllium atoms. Beryllium forms strong bonding with the boron clusters through strong electrostatic and covalent interactions. For instance, the bonding between a beryllium atom and Be3 B12 unit is best described as a Be+ fragment in a 2 P excited state forming a strong and polarized electron-sharing bond with Be3 B12 , followed by several dative interactions by employing its vacant s, p, and very high-lying d orbitals. Counterintuitively, for an s-block element, the p orbitals of beryllium are the most crucial atomic orbitals for bonding rather than s orbitals.

Keywords: Ab Initio Calculations; Beryllium; Bonding; Boron; Doping.