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ISSN 1998-9539

Oxidation of Cobalt(II) Tetraphenylporphyrinate with Molecular Oxygen

Tatyana M. Ziyadova,a@ Vladimir A. Burmistrov,a,b Alexandr S. Semeikin,a and Oskar I. Koifmana,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:
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 CoII 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 CoII 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 СоII + О2 → СоIII reaction have demonstrated that its enthalpy is low and positive, whereas its entropy is high and negative.



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