Sc@B28−, Ti@B28, V@B28+, and V@B292−: Spherically Aromatic Endohedral Seashell-like Metallo-Borospherenes

Abstract

Transition-metal-doped boron nanoclusters exhibit unique structures and bonding in chemistry. Using the experimentally observed seashell-like borospherenes C2 B28−/0 and Cs B29− as ligands and based on extensive first-principles theory calculations, we predict herein a series of novel transition-metal-centered endohedral seashell-like metallo-borospherenes C2 Sc@B28− (1), C2 Ti@B28 (2), C2 V@B28+ (3), and Cs V@B292− (4) which, as the global minima of the complex systems, turn out to be the boron analogues of dibenzenechromium D6h Cr(C6H6)2 with two B12 ligands on the top and bottom interconnected by four or five corner boron atoms on the waist and one transition-metal “pearl” sandwiched at the center in between. Detailed molecular orbital, adaptive natural density partitioning (AdNDP), and iso−chemical shielding surface (ICSS) analyses indicate that, similar to Cr(C6H6)2, these endohedral seashell-like complexes follow the 18-electron rule in bonding patterns (1S21P61D10), rendering spherical aromaticity and extra stability to the systems.