Relations Between Structure and Reactivity in Free‐Radical Chemistry

An analysis of the relations between structure and reactivity in free‐radical chemistry has shown that the usual interpretation of reactivities by means of the stability of the radicals involved is greatly simplified and often incorrect. The CX bond energies of the alkanes and simple alkyl derivatives can be explained qualitatively by strain effects in the ground state on the basis of the VSEPR theory and nonbonding interactions. To be able to explain reactivities in free‐radical chemistry, it is necessary to deduce information about the geometry of the transition states during free‐radical formation from experimental measurements. The relations between structure and reactivity in free‐radical chemistry are interpreted in terms of bond dissociation energies, as well as polar and steric effects.