HALOGENATED PEROXYL RADICALS AS MULTIELECTRON OXIDANTS - PULSE-RADIOLYSIS STUDY ON THE REACTION OF TRICHLOROMETHYL PEROXYL RADICALS WITH IODIDE

CCl3OO. radicals are shown to oxidize three equivalents of iodide ions to yield one l2 molecule (showing up as l3 - in aqueous solution) and one l. atom (showing up as l2.-) per peroxyl unit; the mechanism is considered to proceed via a protonated CCl3OO./l- adduct radical as the primary intermediate and subsequent nucleophilic (S(N)2) attack by a second iodide accompanied by electron localization in the hydroperoxide moiety leads to l2 and CCl3O. with the latter being responsible for the oxidation of the third iodide.