Theoretical analysis of trends in hydrogen bonding involving halogen acceptors (F−At) covalently bonded to a group 14 atom (C−Pb)

Abstract

ABSTRACTIn this work, extensive quantum-chemical calculations have been carried out to identify and elucidate trends in the hydrogen-bonding (HB) interaction involving halogen acceptors covalently bonded to a group 14 atom. A series of 25 heterodimers composed of MH3X (where M = C−Pb and X = F−At) and HNC molecules have been selected as model complexes stabilised by the HB interaction occurring between the X atom of MH3X and the H atom of HNC. The interaction energy (Eint) between MH3X and HNC in the MH3X···HNC complexes falls in the range from −2.7 to −10.8 kcal/mol, indicating weak or medium strength of HB in these complexes. The strength of HB in the complexes remains consistent with the well-known HB weakening as X gets heavier. Regarding the effect of M on Eint, the gradual strengthening of HB is observed while descending group 14, but only from M = Si to M = Pb. The trends in Eint are compared with various HB-related parameters obtained from vibrational analysis, the natural bond orbital (NBO) method, the symmetry-adapted perturbation theory (SAPT) and the quantum theory of atoms in molecules (QTAIM). The parameters that present clear (possibly linear) relationships with Eint have been selected to characterise the effect of M and X on the HB interaction.