Noble Gas-Silicon Cations: Theoretical Insights into the Nature of the Bond

The structure, stability, and bonding situation of some exemplary noble gas-silicon cations were investigated at the MP2/aVTZ level of theory. The explored species include the mono-coordinated NgSiX3+ (Ng = He-Rn; X = H, F, Cl) and NgSiF22+ (Ng = He-Rn), the di-coordinated Ar2SiX3+ (X = H, F, Cl), and the “inserted” FNgSiF2+ (Ng = Kr, Xe, Rn). The bonding analysis was accomplished by the method that we recently proposed to assay the bonding situation of noblegas compounds. The Ng-Si bonds are generally tight and feature a partial contribution of covalency. In the NgSiX3+, the degree of the Ng-Si interaction mirrors the trends of two factors, namely the polarizability of Ng that increases when going from Ng = He to Ng = Rn, and the Lewis acidity of SiX3+ that decreases in the order SiF3+ > SiH3+ > SiCl3+. For the HeSiX3+, it was also possible to catch peculiar effects referable to the small size of He. When going from the NgSiF3+ to the NgSiF22+, the increased charge on Si promotes an appreciable increase inthe Ng-Si interaction, which becomes truly covalent for the heaviest Ng. The strength of the bond also increases when going from the NgSiF3+ to the “inserted” FNgSiF2+, likely due to the cooperative effect of the adjacent F atom. On the other hand, the ligation of a second Ar atom to ArSiX3+ (X = H, F, Cl), as to form Ar2(SiX3+), produces a weakening of the bond. Our obtained data were compared with previous findings already available in the literature.