Noncovalent Bond between Tetrel π-Hole and Hydride
Author ORCID Identifier
Qingzhong Li https://orcid.org/0000-0003-1486-6772
Steve Scheiner https://orcid.org/0000-0003-0793-0369
Physical Chemistry Chemical Physics
Royal Society of Chemistry
NSF, Division of Chemistry (CHE) 1954310
NSF, Division of Chemistry (CHE)
The π-hole above the plane of the X2T′Y molecule (T′ = Si, Ge, Sn; X = F, Cl, H; Y = O, S) was allowed to interact with the TH hydride of TH(CH3)3 (T = Si, Ge, Sn). The resulting TH⋯T′ tetrel bond is quite strong, with interaction energies exceeding 30 kcal mol−1. F2T′O engages in the strongest such bonds, as compared to F2T′S, Cl2T′O, or Cl2T′S. The bond weakens as T′ grows larger as in Si > Ge > Sn, despite the opposite trend in the depth of the π-hole. The reverse pattern of stronger tetrel bond with larger T is observed for the Lewis base TH(CH3)3, even though the minimum in the electrostatic potential around the H is nearly independent of T. The TH⋯T′ arrangement is nonlinear which can be understood on the basis of the positions of the extrema in the molecular electrostatic potentials of the monomers. The tetrel bond is weakened when H2O forms an O⋯T′ tetrel bond with the second π-hole of F2T′O, and strengthened if H2O participates in an OH⋯O H-bond.
Liu, Na, et al. “Noncovalent Bond between Tetrel π-Hole and Hydride.” Physical Chemistry Chemical Physics, vol. 23, no. 17, 2021, pp. 10536–44. DOI.org (Crossref), https://doi.org/10.1039/D1CP01245B.