Reactions of halogenoaliphatic acids with free radicals in aqueous solution. Part III. Reactions with inorganic free radicals

Abstract

The ions CO₂^–, Cd⁺, Ni⁺, Co⁺, Al-⁺, Zn⁺, and Mn⁺ were found to induce dehalogenation of ClCH₂·CO₂^–,ClCH₂·CH₂·OH, and BrCH₂·CO₂^–, the order of reactivity being RCl < RBr. On the other hand, N₂O^–, O₂^–, NO₃^2– and Cu⁺, do not induce dehalogenation. Whereas CO₂^– seems to react by a charge-transfer mechanism, the metal ions at their lower state of oxidation seem to react by an inner-sphere mechanism involving halogen atom transfer from the halogenoaliphatic compound.