Oxidation of Cobalt(II) Tetraphenylporphyrinate with Molecular Oxygen

被引：3
|
作者：
Ziyadova, Tatyana M. [1 ]
Burmistrov, Vladimir A. [1 ,2 ]
Semeikin, Alexandr S. [1 ]
Koifman, Oskar I. [1 ,2 ]
机构：
[1] Ivanovo State Univ Chem & Technol, Res Inst Macroheterocycles, Ivanovo 153000, Russia
[2] Russian Acad Sci, GA Krestov Inst Solut Chem, Ivanovo 153045, Russia
来源：
MACROHETEROCYCLES | 2015年 / 8卷 / 03期
基金：
俄罗斯基础研究基金会;
关键词：
Metalloporphyrin; mu-peroxodimer; oxidation; ion pair; CO(II);
D O I：
10.6060/mhc140926z
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
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 mu-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 Co-II + O-2 -> Co-III reaction have demonstrated that its enthalpy is low and positive, whereas its entropy is high and negative.
引用
收藏
页码：274 / 278
页数：5
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