Evidence for electron transfer, radical and ionic pathways in the decomposition of diacyl peroxide
Abstract
The thermal decomposition mechanism of 4,4-dimethylpentanoyl m-chlorobenzoyl peroxide and its α- and β-dideuteriated analogues is described. Product analyses and CIDNP studies suggest that all three pathways, electron transfer, radical and ionic, are operative in decomposition of these peroxides. Two pulsed-NMR techniques have been employed to eliminate distortions of CIDNP intensities arising from spin–lattice relaxation. These quantitative CIDNP studies have revealed an additional pure ionic pathway which competes with the radical pair electron transfer pathway to form rearranged reaction products.