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Nature and Strength of M–H···S and M–H···Se (M = Mn, Fe, & Co) Hydrogen Bond

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journal contribution
posted on 25.02.2019 by Dipak Kumar Sahoo, Subhrakant Jena, Juhi Dutta, Abhijit Rana, Himansu S. Biswal
The significance of dispersion contribution in the formation of strong hydrogen bonds (H-bonds) can no more be ignored. It was illustrated that less electronegative and electropositive H-bond acceptors such as S, Se, and Te are also capable of forming strong N–H···Y H-bonds, mostly due to the high polarizabilities of H-bond acceptor atoms. Herein, for the first time, we report the evidence of formation of nonconventional M-H···Y H-bonds between metal hydrides (M-H, M = Mn, Fe, Co) and chalcogen H-bond acceptors (Y = O, S, or Se). The nature and the strength of unusual M-H···Y H-bonds were revealed by several quantum chemical calculations and H-bond descriptors. The structural parameters, electron density topology, donor–acceptor natural bond orbital (NBO) interaction energies, and spectroscopic observables such as M-H stretching frequencies and 1H chemical shifts are well-correlated to manifest the existence and strength of M-H···Y H-bonding. The M-H···Y H-bonds are dispersive in nature, and the computed H-bond energies are found to be in the range from ∼5 to 30 kJ/mol, which can be compared to those of the conventional H-bonds such as O–H···O, N–H···O, and N–H···OC H-bonds, etc.