ELECTRON SPIN RESONANCE STUDY OF PHOSPHORANYL RADICALS I. INFLUENCE OF STERIC AND ELECTRONIC EFFECTS ON RADICAL FORMATION IN SOLUTION

Abstract

An electron spin resonance study of phosphoranyl radicals, generated by u.v. irradiation of solutions containing a trialkylphosphite and a dialkylperoxide, enabled us to examine the influence of steric and electronic factors on radical formation. It was demonstrated that the influence of steric factors, such as α- or β-branching of the alkyl groups, on the magnitude of radical formation was present in both trialkyl- and methyldialkylphosphites, but not in dimethylalkylphosphites. Furthermore, the study of additional hetero atoms in the alkyl ligand of the dimethylalkylphosphites clearly revealed the influence of the gauche-effect. It was demonstrated that the presence of the gauche-effect, which causes a conformational preference in which a larger steric hindrance is produced, resulted in a decrease of radical formation.