Tetrel bonds between PhSiF3/PhTH3 (T = Si, Ge, Sn) and H3ZO (Z = N, P, As): A pentacoordinate silicon (IV) complex

Abstract

AbstractThe nature of the complexes PhTH3H3ZO and PhSiF3H3ZO (T = Si, Ge, and Sn; Z = N, P, and As) has been investigated at the MP2/aug’‐cc‐pVTZ(PP) level. These complexes are primarily stabilized by one T···O tetrel bond. Interaction energies of these complexes vary from 11 to 220 kJ/mol, and T···O separations from 1.89 to 3.09 Å. Charge transfer from the O lone pair into the CT and TH σ* antibonding orbitals leads to the stabilization of these complexes. The T···O tetrel bond between PhTH3/PhSiF3 and H3NO exhibits a significant degree of covalence, characterized by the large interaction energy, negative energy density, and large charge transfer. Furthermore, a pentacoordinate silicon (IV) complex is formed in PhSiF3H3NO with the Si···O distance almost close to the length of SiO bond. This indicates that the oxygen atom in N‐oxides shows a strong affinity to the silicon atom in organosilicon compounds.