Kinetic Evidence for (N,N-Dimethylaniline)-Oxodiperoxomolybdenum(VI) or Tungsten(VI) as Oxidizing Species in Molybdenum(VI) or Tungsten(VI) Catalyzed Hydrogen Peroxide (Perborate) Oxidation of N,N-Dimethylaniline

Perborate in solution affords hydrogen peroxide and the molybdenum(VI) and tungsten(VI) catalyzed oxidations of N,N-dimethylaniline in aqueous acetic acid are first order in the catalysts and second order in the amine. The molybdenum(VI) catalyzed oxidation exhibits Michaelis-Menten type kinetics with respect to the oxidant whereas the tungsten(VI) catalyzed is via two paths, one is first order in the oxidant and the other is independent of [oxidant]. The kinetic results point to (N,N-dimethylaniline)oxodiperoxomolybdenum(VI) and (N,N-dimethyhiline)-oxodiperoxotungsten(VI) and (N,N-dimethylaniline)dioxoperoxotungsten(VI) as oxidizing species.