4.6 Article

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

Journal

MOLECULES
Volume 27, Issue 14, Pages -

Publisher

MDPI
DOI: 10.3390/molecules27144592

Keywords

bonding analysis; electron energy density; noble gas-silicon cations; noble gas complexes; noble gas inserted compounds

Funding

  1. Italian Ministry of Education, University and Research (MIUR)
  2. DIBAF Department of the University of Tuscia through the program Departments of Excellence 2018-2022 (Dipartimenti di Eccellenza 2018-2022), grant Landscape 4.0-food, wellbeing and environment

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In this study, the structure, stability, and bonding situation of noble gas-silicon cations were investigated using theoretical calculations. The results show that the Ng-Si bonds are generally tight and have a partial covalent character. The degree of Ng-Si interaction in NgSiX(3)(+) is influenced by the polarizability of Ng and the Lewis acidity of SiX3+. Peculiar effects related to the small size of He were observed in HeSiX3+. The Ng-Si interaction in NgSiF(2)(2+) increases with the increased charge on Si, and the bond strength also increases in the inserted FNgSiF(2)(+) due to the cooperative effect of the adjacent F atom. On the other hand, the ligation of a second Ar atom to ArSiX3+ weakens 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 NgSiX(3)(+) (Ng = He-Rn; X = H, F, Cl) and NgSiF(2)(2+) (Ng = He-Rn), the di-coordinated Ar2SiX3+ (X = H, F, Cl), and the inserted FNgSiF(2)(+) (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 NgSiX(3)(+), 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 NgSiF(3)(+) to the NgSiF(2)(2+), 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 NgSiF(3)(+) to the inserted FNgSiF(2)(+), 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 Ar-2(SiX3+), produces a weakening of the bond. Our obtained data were compared with previous findings already available in the literature.

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