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KMID : 1059519920360020261
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Journal of the Korean Chemical Society
1992 Volume.36 No. 2 p.261 ~ p.272
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Electrochemical Propertics and Oxidation Reaction of Hydrazobenzene by Oxygen Adducted Tetradentate Schiff Base Cobalt(Ⅱ)(3MeOSED) Activated Catalyst in Aprotic Solvents(Ⅰ)
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Chjo Ki-Hyung
Choi Yong-Kook
Kim Sang-Bock
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Abstract
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Tetradentate Schiff base Cobalt(Ⅱ)(3MeOSED)(H2O)2 complexe was synthesized and allowed to react with dry oxygen to form oxygen adducts of Cobalt(Ⅲ) complexes such as μ-peroxo type [Co(Ⅲ)(3MeOSED)(DMF)]2O2 and [Co(Ⅲ)(3MeOSED)(DMSO)]2O2 in DMF and DMSO or superoxo type [Co(Ⅲ)(3MeOSED)(Py)]O2 in pyridine. The oxygen adducted complex was investigated by cyclic voltammetry and DPP method with glassy carbon electrode in 0.1M TEAP-DMF (-DMSO,-Py) as supporting electrolyte solution. As a result the reduction reaction process occurred to four steps including prewave Of O2- in 1 : 1 oxygen adducted superoxo type [Co(Ⅲ)(3MeOSED)(Py)]O2 complex and three steps not including prewave of O2- in 1 : 2 oxygen adducted μ-peroxo type [Co(Ⅲ)-(3MeOSED)(DMF)]2O2 and [Co(Ⅲ)(3MeOSED)(DMSO)]2O2. A superoxo type [Co(Ⅲ)(3MeOSED)(L)]O2 (L: CH3OH) was generated with oxygen in methanol. Selectively oxidized hydrazobenzene (H2AB) to trans-azobenzene(t-AB) and the rate constant k for oxidation reaction of the following equation is (2.96 ± 0.2) × 10-1M/sec. H2AB + Co (Ⅱ)(3MeOSED)(L)2+O2 ↔ [Co(Ⅲ)(3MeOSED)(L)]O2·H2AB→Co(Ⅱ(3MeOSED)(L)2+t-AB+H2O2.
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KEYWORD
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