Substituent effects on the C-H bond dissociation energy of toluene. A density functional study

The bond dissociation energies of the benzylic C-H bond of a series of 16 para-substituted toluene compounds (p-X-C6H4CH3) have been calculated with the density functional method (BLYP/6-31G*). The calculated substituent effects correlate well with experimental rates of dimerization of parasubstituted alpha,beta,beta-trifluorostyrenes and rearrangement of methylenearylcyclopropanes. Both electron-donating and electron-withdrawing groups reduce the bond dissociation energy (BDE) of the benzylic C-H bond because both groups cause spin delocalization from the benzylic radical center. The calculated spin density variations at the benzylic radical centers correlate well with both the ESR hyperfine coupling constants determined by Arnold et al. and the calculated radical effects of the substituents. The relative radical stabilities are mainly determined by the spin delocalization effect of the substituents, and polar effect of the substituents are not important in the current situation. The ground state effect is also found to influence the C-H BDE.