Comparison for Electron Donor Capability of Carbon-Bound Halogens in Tetrel Bonds

The tetrel bond formed by HC≡CX, H₂C=CHX, and H₃CCH₂X (X=F, Cl, Br, I) as an electron donor and TH₃F (T=C, Si, Ge) was explored by ab initio calculations. The tetrel bond formed by H₃CCH₂X is the strongest, as high as -3.45 kcal/mol for the H₃CCH₂F···GeH₃F dimer, followed by H₂C=CHX, and the weakest bond is from HC≡CX, where the tetrel bond can be as small as -0.8 kcal/mol. The strength of the tetrel bond increases in the order of C < Si < Ge. For the H₃CCH₂X and HC≡CX complexes, the tetrel bond strength shows a similar increasing tendency with the decrease of the electronegativity of the halogen atom. Electrostatic interaction plays the largest role in the stronger tetrel bonds, while dispersion interaction makes an important contribution to the H₂C=CHX complexes.