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Through-space and through-bond mixed charge transfer mechanisms on the hydrazine oxidation by cobalt(II) phthalocyanine in the gas phase.

Two quantum chemistry theoretical models in the gas phase at the density functional theory B3LYP/LACVP(d) level of calculation are proposed to rationalize the hydrazine oxidation by cobalt(II) phthalocyanine (Co(II)Pc). This oxidation reaction involves the net transfer of four electrons. These theoretical models that are described in terms of energy profiles include a through-space mechanism for the transfer of the first electron of the hydrazine and a through-bond mechanism proposed for the transfer of the three electrons remaining. The main difference between both models arises from a one-electron and one-proton alternate transfer for model 1 and a two-electron and two-proton alternate transfer for model 2. The main problem for experimental studies is to determine if the first transfer corresponds to an electron or a chemical transfer. Under this point of view, we proposed two models which deal with this problem. We conclude that model 1 is more reasonable than model 2 because the whole oxidation process is always exergonic.