Anionic complexes of F- and Cl- with substituted methanes: Hydrogen, halogen, and tetrel bonds

摘要

Ab initio MP2/aug'-cc-pVTZ calculations have been carried out to investigate the anionic complexes X : CX(FnH3 n), for X = F, Cl, and n = 0-3. These complexes are stabilized by tetrel, hydrogen, and halogen bonds. Hydrogen-bonded complexes are the most stable complexes and halogen-bonded complexes are the least stable, with one exception. Charge-transfer across intermolecular bonds stabilizes all complexes, and occurs from the anion lone-pair to a sigma* orbital of the substituted methane. EOM-CCSD spin-spin coupling constants (1t)J(X-C) across intermolecular tetrel bonds, (2h)J(C-X) across hydrogen bonds, and (1x)J(Cl-Cl) and (2x)J(C-Cl) across halogen bonds correlate with intermolecular distances. (C) 2016 Elsevier B.V. All rights reserved.