The reactivity of aminoxyls towards peroxyl radicals: an ab initio thermochemical study

Abstract

A thermochemical study has been carried out in order to gain deeper insight into the mechanism with which aminoxyls and peroxyl radicals react together. CBS-QB3 has been chosen from the ab initio high accuracy energy methods available. Different mechanisms are discussed and the thermodynamic quantities computed for each species involved in the different reaction steps. The results from this study suggest a mechanism involving a radical–radical coupling between aminoxyl and peroxyl with formation of an unstable amino trioxide that may decompose yielding dioxygen and the corresponding alkoxyamine. The latter derivative can undergo C–O bond cleavage forming the starting aminoxyl, which along with dioxygen represents the main reaction product.