The competition and cooperativity of hydrogen/halogen bond and π-hole bond involving the heteronuclear ethylene analogues.

The noncovalent interactions involving heteronuclear ethylene analogues H2 CEH2 (E = Si, Ge and Sn) have been studied by the Møller-Plesset perturbation theory to investigate the competition and cooperativity between the hydrogen/halogen bond and π-hole bond. H2 CEH2 has a dual role of being a Lewis base and acid with the region of π-electron accumulation above the carbon atom and the region of π-electron depletion (π-hole) above the E atom to participate in the NCX···CE (X = H and Cl) hydrogen/halogen bond and CE···NCY (Y = H, Cl, Li and Na) π-hole bond, respectively. When HCN/ClCN interacts with H2 CEH2 by two sites, the strength of hydrogen bond/halogen bond is stronger than that of π-hole bond. The π-hole bond becomes obviously stronger when the metal substituent of YCN (Y = Li and Na) interacting with H2 CEH2 , showing the character of partial covalent, its strength is much greater than that of hydrogen/halogen bond. In the ternary complexes, both hydrogen/halogen bond and π-hole bond are simultaneously strengthened compared to those in the binary complexes, especially in the systems containing alkali metal.