title: Ab initio evaluation of intramolecular electron transfer reactions in halobenzenes and stabilized derivatives.
abstract: 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 pi acceptors, is compared to that shown by the unsubstituted halobenzenes (PhX, X = F, Cl, Br, I). The presence of pi and sigma radical anions was inspected as well as the intramolecular electron transfer (intra-ET) from the pi to the sigma 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 sigma surface exerted by the different halogens and its effect on the rate constants for dissociation are explained.
authors: INFIQC, Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, 5000 Córdoba, Argentina. adriana@dqo.fcq.unc.edu.ar
authors: Adriana B
authors: AB
authors: Pierini
authors: D Mariano A
authors: DM
authors: Vera