Halogenated peroxyl radicals as multi-electron oxidants: pulse radiolysis study on the reaction of trichloromethyl peroxyl radicals with iodide

Abstract

CCl₃OO˙ radicals are shown to oxidize three equivalents of iodide ions to yield one I₂ molecule (showing up as I₃^– in aqueous solution) and one I˙ atom (showing up as I₂˙^–) per peroxyl unit; the mechanism is considered to proceed via a protonated CCl₃OO˙I^– adduct radical as the primary intermediate and subsequent nucleophilic (S_N2) attack by a second iodide accompanied by electron localization in the hydroperoxide moiety leads to I₂ and CCl₃O˙ with the latter being responsible for the oxidation of the third iodide.