Theory of Intramolecular Electron Transfer Reactions in Anion Radicals of Nitrobenzyl Halides

Article abstract of DOI:10.1021/j100249a006

Recently, we have suggested a lattice-based theory of chemical reactivity in which quantum and statistical mechanical arguments are combined to yield a method for calculating rate constants for certain classes of reactions.We present here the first concrete application of this theory and calculate the first-order rate constants for dehalogenation of the ortho-, meta-, and para-substituted nitrobenzyl chloride anion radicals.Our theoretical results are obtained by calculating the ? orbital spin populations of the anion radicals (MO calculations using the GAUSSIAN 82 series of programs), using the consequent values to distinguish the ortho, meta, and para sites, and then calculating the rate constants using a lattice statistical approach, the latter based on a theory presented recently.Apart from the limitations of the MO calculations and the neglect of solvent effects, the method involves no further assumptions or parameters.The theoretical estimates are in good agreement with the experimental rate constants.