Ab Initio Evaluation of Intramolecular Electron Transfer Reactions in Halobenzenes and Stabilized Derivatives

The potential energy surfaces for the fragmentation of the radical anions of p-nitrochlorobenzene and p- and m-chloroacetophenones were explored using first principle methods. The behavior of these compounds, stabilized by π acceptors, is compared to that shown by the unsubstituted halobenzenes (PhX, X = F, Cl, Br, I). The presence of π and σ radical anions was inspected as well as the intramolecular electron transfer (intra-ET) from the π to the σ surface, responsible for the dissociation of these intermediates. The profiles obtained with the B3LYP functional in the gas phase and in the presence of a polar solvent are in agreement with the spectroscopic evidence and with the experimentally observed reactivity of the compounds under study. The stability of the radical anion of p-nitrochlorobenzene and the adiabatic and endothermic nature of its dissociation are explained. The order of the rate constants for dissociation m-chloroacetophenone < p-chloroacetophenone is interpreted on the basis of the differences in the adiabatic character of the intra-ET of both isomers which is ascribed to the nodal properties of their SOMOs. In the halobenzene family, the electronic factors responsible for the intra-ET are analyzed. The stabilization of the σ surface exerted by the different halogens and its effect on the rate constants for dissociation are explained.