Superstrong Chemical Bonding of Noble Gases with Oxidoboron (BO+) and Sulfidoboron (BS+)

Inspired by the overwhelming exploration of noble gas–boron (Ng–B) bond containing chemical compounds, the stability of the Ng bound BY+ and AlY+ (Y = O and S) has been investigated by using various ab initio based quantum chemical methods. Ng atoms are found to form exceptionally strong bonds with BO+ species in the predicted NgBO+ (Ng = He–Rn) complexes with remarkably high Ng–B dissociation energies ranging from 138.0 to 462.2 kJ mol–1 for the He–Rn series. It is the highest ever Ng–B binding energy in conjunction with the smallest Ng–B bond length for any of the cationic species involving a Ng–B bond as reported until today. More importantly, the calculated Ng–B bond lengths have been found to be much lower than the respective covalent limits in both NgBO+ and NgBS+ ions. The electronegativity difference between O and S atoms has been reflected nicely in the Ng–B and Ng–Al binding energies, which are found to be 91.9–346.5, 9.6–169.2, and 6.8–142.1 kJ mol–1 in NgBS+, NgAlO+, and NgAlS+, respectively. The strong covalent bonding between Ng and B/Al atoms in the predicted chemical systems has also been supported by the natural bonding orbital (NBO) and electron density based atoms-in-molecule (AIM) analysis. In addition, the energy decomposition analysis (EDA) in combination with the natural bond orbital for chemical valence (NOCV) indicates that the orbital interaction term is the prime contributor to the total attraction energy in the Ng–B and Ng–Al bonds. Furthermore, Ng–B and Ng–Al bonding can be assessed using the donor–acceptor model where the σ-electron donation that takes place from Ng (HOMO) → XY+ (LUMO) (X = B and Al; Y = O and S) is the major contributor to the orbital interaction energy. All the computational results along with the very recent experimental observation of ArOH+ and NgMX (Ng = Ar–Xe; M = Cu, Ag, Au; X = F, Cl) clearly indicate that it might be possible to synthesize and characterize these superstrong complexes, NgXY+ (Ng = He–Rn; X = B and Al; Y = O and S), under suitable experimental technique(s).