A-H…σ Hydrogen Bonds: Dihydrogen and Cycloalkanes as Proton Acceptors

Abstract

ωB97XD/aug-cc-pVTZ calculations were performed for complexes of dihydrogen, cyclopropane, cyclobutane and cyclopentane, with simple proton donating species such as hydrogen fluoride, hydrogen chloride, water, hydrogen cyanide and acetylene. Numerous dependencies between geometrical, energetic and topological parameters of complexes considered were found, since various theoretical approaches were applied: Quantum Theory of 'Atoms in Molecules' (QTAIM), Natural Bond Orbital (NBO) method and energy decomposition analysis (EDA). It was confirmed that complexes of dihydrogen and cyclopropane are linked through the A-H…σ interactions that may be classified as hydrogen bonds. In the case of complexes of cyclobutane such hydrogen bonds are rather weak. Other type and also weak A-H…C hydrogen bonds are formed for complexes with cyclopentane.

Keywords: A−H…σ hydrogen bond; Natural Bond Orbital (NBO) method; Quantum Theory of ‘Atoms in Molecules’ (QTAIM); electrostatic potential; energy decomposition analysis (EDA).