ArticlesKinetics and mechanism of the oxidative dehydrogenation of 1,2-Diphenylhydrazine (cas 122-66-7) with molecular O2 catalyzed by triphenylphosphinecobaloxime(II)

Add time:09/08/2019    Source:sciencedirect.com

1,2-Diphenylhydrazine (cas 122-66-7) (H2AB) is catalytically oxidized to azobenzene (AB) in the presence of triphenylphosphinecobaloxime(II), Cox, at 1 bar O2 and 30 °C. The catalytic reaction does not involve H2O2 as intermediate or product, and its rate is independent of the O2-pressure. The rate law is of the form: Win = k3K2[Cox]0[H2AB](1 + K2[H2AB]) The kinetic behaviour is interpreted by a mechanism in which superoxo-cobaloxime(III), H-bonded to H2AB, transfers an oxygen atom to form H2O 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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