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

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