Kinetics and mechanism of electron transfer reactions in acetate buffers: Ruthenium (III) chloride catalysed oxidation of nitrite by thallium (III) acetate

Despite thallium (III) acetate being a potential oxidant and a reagent fo r a large number of sy ntheti c app lications, the reactivity of acetatothallium (Ill) species towards inorganic substrates has not been ex plored much. Thallium (III) acetate in acetic acid oxidizes olefins to I, I-and I, 2-diacetalsl.2. Oulette and co-workers) reported the kinetics of the oxidative cleavage of ary I cyclopropanes by thalliu m (Il l) acetate ascribing TI (OAc)3 to be the most electrophilic species. T I (OAc)3 has also been considered to be a reactive species in the oxidation of alcohols4. However, Henri considered Tl (OAch+ to be the reactive form of thallium (III) in acetic acid. The in teresting preliminary results of the oxidation of nitrite by thalliurri (m ) in acetate buffers prompted us to probe the reaction mechani sm. Also the reactivity pattern of acetatothallium (III) species can be analysed exclusively in such a system where the substrate remai ns unaffected by the acetate ions in acetate buffers.