Directionality of Dihydrogen Bonds: The Role of Transition Metal Atoms
作者： Oleg A. Filippov , Natalia V. Belkova , Lina M. Epstein , Agusti Lledos , Elena S. Shubina
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摘要: A theoretical study on two series of electron-rich group 8 hydrides is carried out to evaluate involvement the transition metal in dihydrogen bonding. To this end, structural and electronic parameters are computed at DFT/B3PW91 level for hydrogen-bonded adducts [(PP(3))MH(2)] [Cp*MH(dppe)] (M = Fe, Ru, Os; PP(3) κ(4)-P(CH(2)CH(2)PPh(2))(3), dppe κ(2)-Ph(2)PCH(2)CH(2)PPh(2)) with CF(3)CH(2)OH (TFE) as proton donor. The results compared those adduct [Cp(2)NbH(3)]⋅TFE featuring a "pure" bond, classical hydrogen bonds pyridine⋅TFE Me(3)N⋅TFE. Deviation H⋅⋅⋅H-A fragment from linearity shown originate participation latter confirmed by obtained NBO AIM analysis. Considered together, orbital interaction energies bond ellipticity salient indicators effect allow MH⋅⋅⋅HA be described bifurcate bond. impact M⋅⋅⋅HA increase descending group, explains experimental trends mechanisms proton-transfer reactions via intermediates. Strengthening M⋅⋅⋅H case 5d leads direct transfer atom.
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