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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 35, Number 6
JKCSEZ 35(6)
December 20, 1991 

Selective Oxidation of 2,6-di-tert-butylphenol by Oxygen Adducted Pentadentate Schiff Base Cobalt (Ⅱ) Activated Catalysts and Electrochemical Properties of Cobalt (Ⅱ) Catalysts in Aprotic Solvents

비수용매에서 산소첨가된 다섯자리 Schiff Base Cobalt (Ⅱ) 활성촉매들에 의한 2,6-di-tert-butylphenol의 선택산화와 전기화학적 성질
Ki-Hyung Chjo, Yong-Kook Choi, Sang-Bock Kim, Song-Ju Lee, Jong-Soon Kim

조기형, 최용국, 김상복, 이송주, 김종순
산소가 포화된 DMF 용매에서 다섯자리 Schiff base cobalt(Ⅱ) 착물들의 균일 산화촉매에 의한 2,6-di-tert-butylphenol의 산화주생성물은 2,6-di-tert-butylbenzoquinone(BQ)이고, 이들 균일 할성촉매는 DMSO와 pyridine 용매에서 PVT법에 의한 O2/Co 몰결합비가 1:1인 superoxo형인 [Co(Ⅲ)(sal-DET)]O2와 [Co(Ⅲ)(sal-DPT)]O2이나 DMF 용매에서는 1:1.52이고 고체상태에서는 1:2인 μ-peroxo형으로 주어진다. 또한 0.1M TEAP-DMSO와 0.1 M TEAP-Py의 지지전해질 용액에서 유리질 탄소전극을 사용한 순한전압전류법과 DPP법에 의한 superoxo형인 균일산화 활성 촉매들의 전기화학적 특성은 O2-의 prewave을 포함한 네단계 환원과정으로 일어난다.

Activated oxidation catalysts are generated by the treatment of pentadentate Schiff base cobalt(Ⅱ) complexes with the oxygen saturated DMF solution. Oxidation of 2,6-di-tert-butylphenol by homogeneous oxidation catalysts of superoxo type pentadentate schiff base cobalt(Ⅲ) complexes yields 2,6-di-tert-butylbenzoquinone(BQ) as a major product. And O2/Co mole ratio of homogeneous oxidative catalysts such as [Co(Ⅲ)(sal-DET)]O2 and [Co(Ⅲ)(sal-DPT)]O2 by PVT method of the oxygen absorption in DMSO and pyridine solution was 1:1, 1:1.52 in DMF solution and μ-peroxo type cobalt(Ⅲ) complexes formed at solid state. The redox reaction processes of superoxo type cobalt(Ⅲ) complexes as homogeneous oxidation catalysts were investigated by cyclic voltammetry and DPP method at a glassy carbon electrode. As a result of electrochemical measurements the reduction processes of oxygen adducted superoxo type cobalt(Ⅲ) complexes occurred to four steps including prewave of O2-in 0.1M TEAP-DMSO and 0.1 M TEAP-Pyridine as supporting electrolyte solution.

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