Interactions in Model Ionic Dyads and Triads Containing Tetrel Atoms

The interactions in model ionic YTX₃···Z (Y = NC, F, Cl, Br; X = F, Cl, Br, Z = F^-, Cl^-, Br^-, Li⁺) dyads containing the tetrel atoms, T = C, Si, Ge, were studied using ab initio computational methods, including an energy decomposition analysis, which found that the YTX₃ molecules were stabilized by both anions (via tetrel bonding) and cations (via polarization). For the tetrel-bonded dyads, both the electrostatic and polarization forces make comparable contributions to the binding in the C-containing dyads, whereas, electrostatic forces are by far the largest contributor to the binding in the Si- and Ge-containing analogues. Model metastable Li⁺···NCTCl₃···F^- (T = C, Si, Ge) triads were found to be lower in energy than the combined energy of the Li⁺ + NCTCl₃ + F^- fragments. The pair energies and cooperative energies for these highly polar triads were also computed and discussed.