Chem. Phys. Lett. 655-656, 115–119 (2016)

DOI: 10.1016/j.cplett.2016.05.030


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

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 σ orbital of the substituted methane. EOM-CCSD spin-spin coupling constants 1tJ(X-C) across intermolecular tetrel bonds, 2hJ(C-X) across hydrogen bonds, and 1xJ(Cl-Cl) and 2xJ(C-Cl) across halogen bonds correlate with intermolecular distances.