Theoretical studies on the dihydrogen bonding between shortchain hydrocarbon and magnesium hydride

Abstract

The C—H…H dihydrogen-bonded complexes of methane, ethylene, acetylene, and their derivatives with magnesium hydride were systematically investigated at MP2/aug-cc-PVTZ level. The results confirm that the strength of dihydrogen bonding increases in the following order of proton donors: C(sp ³)—H<C(sp ²)—H<C(sp)—H and chlorine substituents enhance the C—H…H interaction. In the majority of the complexes with a cyclic structure, the Mg—H proton-accepting bond is more sensitive to the surroundings than C—H proton-donating bond. The nature of the electrostatic interaction in these C—H…H dihydrogen bonds was also unveiled by means of the atoms in molecules(AIM) analysis. The natural bond orbital(NBO) analysis suggests that the charge transfer in the cyclic complexes is characteristic of dual-channel. The direction of the net charge transfer in the cyclic complexes is contrary to that previously found in dihydrogen bonded systems.

Keywords

Dihydrogen bond / Atom in molecule(AIM) theory / Bond critical point / Natural bond orbital(NBO) / Charge transfer

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