Delocalization model of regioselectivity and reactivity of free radicals in reactions of addition to olefins

On the basis of the concept of polarity (philicity) of free radicals as proposed by the authors, within the framework of methods of qualitative surfaces of potential energy (linear combinations of configurations of fragments) and stabilization energy, an effective model has been developed for the regioselectivity and reactivity of radicals in processes of addition. A critical examination is made of certain key aspects of the change in regiochemistry and reactivity with changes in the electronic structure of the free radical and substrate. The dominant trends in regioselectivity and reactivity in processes of free-radical addition to olefins are controlled by electronic effects and can be predicted by analyzing interactions of diabatic potential energy surfaces or orbital interactions for a system consisting of a free radical and an unsaturated substrate.Presented at 3rd All-Union Symposium Dynamics of Elementary Atomic-Molecular Processes (Chernogolovka, June 1985) and at the 9th All-Union Conference on Quantum Chemistry (Ivanovo, June 1985).Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 23, No. 2, pp. 135–148, March–April, 1987.The authors are grateful to M. V. Bazilevskii for his constructive discussion of the results obtained in this work.