Intrinsic Barriers to Proton Exchange between Transition-Metal Centers: Application of a Weak-Interaction Model

Article abstract of DOI:10.1021/ja00216a014

A weak-interaction model for proton self-exchange between transition-metal centers is considered.The rate constant obtained from the Fermi golden-rule expression of radiationless transition theory is a product of terms for assembling acid and base reactants at the correct orientation and distance, a classical reaction frequency, an electron-proton reaction probability, and classical nuclear factors deriving from the requirement for reorganization of ancillary ligands and solvent modes.It is found that such a model yields calculated rate constants and activation parameters in reasonable agreement with the experimental data, provided that the fluxionality of certain metal centers is taken into account.