Prediction and characterization of a chalcogen–hydride interaction with metal hybrids as an electron donor in F2CS–HM and F2CSe–HM (M = Li, Na, BeH, MgH, MgCH3) complexes

Abstract

A novel type of σ-hole bonding has been predicted and characterized in F₂CS–HM and F₂CSe–HM (M = Li, Na, BeH, MgH) complexes at the MP2/aug-cc-pVTZ level. This interaction, termed a chalcogen–hydride interaction, was analyzed in terms of geometric, energetic and spectroscopic features of the complexes. It exhibits similar properties to hydrogen bonding and halogen bonding. The methyl group in metal hydrides makes a positive contribution to the formation of chalcogen–hydride bonded complexes. In the F₂CSe–HLi–OH₂ complex, the chalcogen–hydride bonding shows synergetic effects with lithium bonding. These complexes have been analyzed with the atoms in molecules (AIM) theory and symmetry adapted perturbation theory (SAPT) method. The results show that the chalcogen–hydride bonding is dominated with an electrostatic interaction.