Oxidation of Cobalt(II) Tetraphenylporphyrinate with Molecular Oxygen

Tatyana M. Ziyadova,^a@ Vladimir A. Burmistrov,^a,b Alexandr S. Semeikin,^a and Oskar I. Koifman^a,b

^aResearch Institute of Macroheterocycles, Ivanovo State University of Chemistry and Technology, 153000 Ivanovo, Russian Federation

^bG.A. Krestov Institute of Solution Chemistry, Russian Academy of Sciences, 153045 Ivanovo, Russian Federation

^@Corresponding author E-mail: ziyadova_tm@mail.ru

The state of cobalt complexes with tetraphenylporphyrin in alcoholic solutions has been studied by means of conductometry and electronic absorption spectroscopy. In the presence of oxygen, the Co^II complex is oxidized into the µ-peroxodimer and chloro(tetraphenylporphyrinato)cobalt(III), the latter exists in the form of the solvent-separated ion pair. Kinetic experiments have revealed conditions of the products formation in the course of the Co^II complex oxidation. It has been demonstrated that only chloro(tetraphenylporphyrinato)cobalt(III) oxidizes thiols in the presence of oxygen. The elucidated kinetic and activation parameters of the Со^II + О₂ → Со^III reaction have demonstrated that its enthalpy is low and positive, whereas its entropy is high and negative.

References:

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