대한화학회지 (Journal of the Korean Chemical Society)

  • 제35권6호
  • /
  • Pages.689-698
  • /
  • 1991
  • /
  • 1017-2548(pISSN)
  • /
  • 2234-8530(eISSN)
대한화학회 (Korean Chemical Society)
권호 표지

비수용매에서 산소첨가된 다섯자리 Schiff Base Cobalt (Ⅱ) 활성촉매들에 의한 2,6-di-tert-butylphenol의 선택산화와 전기화학적 성질

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

  • 조기형 (전남대학교 자연과학대학 화학과) ;
  • 최용국 (전남대학교 자연과학대학 화학과) ;
  • 김상복 (울산대학교 자연과학대학 화학과) ;
  • 이송주 (전남대학교 자연과학대학 화학과) ;
  • 김종순 (전남대학교 자연과학대학 화학과)
  • Chjo, Ki-Hyung (Department of Chemistry, College of Natural Science, Chonnam National University) ;
  • Choi, Yong-Kook (Department of Chemistry, College of Natural Science, Chonnam National University) ;
  • Kim, Sang-Bock (Department of Chemistry, Ulsan University) ;
  • Lee, Song-Ju (Department of Chemistry, College of Natural Science, Chonnam National University) ;
  • Kim, Jong-Soon (Department of Chemistry, College of Natural Science, Chonnam National University)
  • 발행 : 19911100
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초록

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 활성촉매는 DMSO와 pyridine 용매에서 PVT법에 의한 $O_2$/Co 몰결합비가 1:1인 superoxo형인 [Co(Ⅲ)(sal-DET)]$O_2$와 [Co(Ⅲ)(sal-DPT)]$O_2$이나 DMF 용매에서는 1:1.52이고 고체상태에서는 1:2인 ${\mu}$-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 $O_2$-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 $O_2$/Co mole ratio of homogeneous oxidative catalysts such as [Co(Ⅲ)(sal-DET)]$O_2$ and [Co(Ⅲ)(sal-DPT)]$O_2$by PVT method of the oxygen absorption in DMSO and pyridine solution was 1:1, 1:1.52 in DMF solution and ${\mu}$-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 $O_2$-in 0.1M TEAP-DMSO and 0.1 M TEAP-Pyridine as supporting electrolyte solution.

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