Abstract
A model of selective energy transfer, originally developed for catalysis, is applied to explain the isokinetic temperature found for some substitution (and exchange) reactions of the hexasolvated complex of Ni(II) in dimethyl sulfoxide solutions. An analysis of the stepwise change of activation energies for these and similar reactions indicates that the threefold degenerate Ni-O stretching vibration is involved in the activation process. The reaction coordinate can be described as an expansion of one face of the octahedron, where the reactant enters, and the corresponding contraction of the opposite face.
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