Collect. Czech. Chem. Commun. 1983, 48, 2469-2472

PMO treatment of structure-reactivity relationships. Polar effects in the free radical addition reactions

Robert Ponec, Milan Hájek and Jaroslav Málek

Institute of Chemical Process Fundamentals, Czechoslovak Academy of Sciences, 165 02 Prague 6-Suchdol


The electronic nature of free radicals in the addition to substituted styrenes was studied by a simple perturbation approach utilizing delocalisability Dr as a static index of reactivity. In agreement with experimental results, the calculations reproduce correctly the change in the sign of the Hammett ρ constants in going from electronegative to electropositive radicals.