Abstract
1,2-Diphenylhydrazine (H 2AB) is catalytically oxidized to azobenzene (AB) in the presence of triphenylphosphinecobaloxime(II), Cox, at 1 bar O 2 and 30 °C. The catalytic reaction does not involve H 2O 2 as intermediate or product, and its rate is independent of the O 2-pressure. The rate law is of the form: W in = k 3 K 2[Cox] 0[H 2AB] (1 + K 2[H 2AB]) The kinetic behaviour is interpreted by a mechanism in which superoxo-cobaloxime(III), H-bonded to H 2AB, transfers an oxygen atom to form H 2O and a reactive oxocobaloxime(IV). The latter brings about fast two-equivalent oxidation to re-form the active cobaloxime(II) catalyst.
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