Manganese(III) oxidations of benzoylhydrazine,aroxyacetylhydrazine, semicarbazide,thiosemicarbazide and their derivatives in pyrophosphate media

Manganese(III) ion was stabilised in weakly acidic solution by means of pyrophosphate. Conditions for the quantitative oxidation of hydrazine, benzoylhydrazines, aroxyacetylhydrazines, semicarbazide, semicarbazones, thiosemicarbazide and thiosemicarbazones were investigated by titrimetric and potentiometric methods. The stoichiometries of these oxidations were pH-dependent. At pH 5 benzoyl hydrazines were oxidised by donating two electron each, the nitro derivative being the sole exception to show a three-electron change. Aroxyacetylhydrazines, semicarbazide and semicarbazones underwent three-electron oxidations. The free radical nature of these reactions was illustrated. Thiosemicarbazides reacted faster than semicarbazides. Metal complexes of thiosemicarbazide also yielded stoichiometric results, indicative of the number of TSC ligands in the complex. The oxidation products have been identified. At pH 1 these reactions conformed to different stoichiometries.