Abstract
Quantum chemical calculations have been performed to investigate the structure, stability, and bonding in noble gas (Ng) bound Be2B5+ complexes. The present results show that Be2B5+, a charge-separated [Be]2+[B5]3−[Be]2+ cluster, can employ both its cationic Be center and anionic B center to bind Ng atoms. It can bind a total of seven Ng atoms, resulting in the formation of a highly symmetric (NgBe)2Be2(NgB)5B5+ complex, having D5h point group. The thermochemical analyses reveal that the Ng-Be bonds are stronger than the Ng-B bonds. (NgBe)2Be2B5+ (Ng = Ar-Rn) complexes are stable against the dissociation of Ng atoms even at room temperature. But, (NgBe)2Be2B5+ (Ng = He and Ne) and (NgBe)2Be2(NgB)5B5+ (Ng = Ar-Rn) complexes are stable only at very low temperatures. Therefore, they can be suitable candidates for low-temperature matrix isolation. A thorough bonding analysis, through charge and energy decomposition methods, discloses that despite the Ng-B interaction being weaker than the Ng-Be interaction, the former bond is more covalent than the latter one. In fact, in the Ng-B bonds, both the orbital and electrostatic interactions are larger in magnitude than the Ng-Be bonds; however, significantly larger Pauli repulsion in the former bonds makes them weaker than the latter bonds. In both Ng-Be and Ng-B bonds, the covalent interaction originates from a strong Ng(pσ) → Be2B5+ σ donation, complemented by two weak Ng(pπ) → Be2B5+ π donations.