A theoretical analysis of the kinetics of reductive cleavage of the carbon—halogen bond in tert-butyl halides in polar solvent

Abstract

Rate constants and activation energies of dissociative electron transfer reactions of t-butyl halides proceeding in polar solvent are calculated. A model is used in which potential energy of the bond C-X to be broken is described by a Morse function in reactant and an exponential curve in product. The parameters of the exponential function are taken from quantum chemical calculations of the radical anions of t-butyl halides. The reorganization energy of reaction is computed in the framework of the cavity model. Results of calculations are compared with experimental data.