Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Selective Oxidation of 2,6-di-tert-butylphenol and Electrochemical Properties by Oxygen Adducted Tetradentate Schiff Base Cobalt (Ⅲ) Activated Catalysts in Aprotic Solvents

비수용매에서 산소 첨가된 네자리 Schiff Base Cobalt(Ⅲ) 활성 촉매들에 의한 2,6-di-tert-butylphenol의 선택 산화와 전기화학적 성질

  • 조기형 (전남대학교 화학과) ;
  • 최용국 (전남대학교 자연과학대학 화학과) ;
  • 함희석 (전남대학교 화학과) ;
  • 김상복 (울산대학교 자연과학대학 화학과) ;
  • 서성섭 (전남대학교 자연과학대학 화학과)
  • Published : 19901100
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Abstract

It is generated in DMF by activated catalysts of superoxo cobalt(III) complex, such as [Co(III)(Schiff base)(L)]O$_2$ (Schiff base; SED, SOPD and o-BSDT, L; DMF and Py) which mole ratio of oxygen to metal is 1:1 that oxidation major product of 2,6-di-tert-butylphenol by homogeneous oxidatve catalysts of oxygen adducted tetradentate Schiff base cobalt(III) is 2,6-ditert-butylbenzoquinone (BQ). And oxidation product of 3,3',5,5'-tetra-tert-butyldiphenoquinone (DPQ) is generated by activated catalysts such as $\mu$-peroxo cobalt(III) complex; $[Co(III)(SND)(L)]_2$$O_2$ (L; DMF and Py) which mole ratio of oxygen to metal is 1:2. It is difficult to identify these homogeneous activated catalysts such as superoxo and $\mu$-peroxo cobalt(III) complexes in DMF and DMSO solvents. But we can identify by P.V.T method of the oxygen absorption in pyridine solvent and by the reduction process occurred to four steps including prewave of O$_2$- in 1:1 oxygen adducted superoxo cobalt(III) complexes and three steps not including prewave of O$_2$- in 1:2 oxygen adducted $\mu$-peroxo cobalt(III) complexes by the cyclic voltammetry with glassy carbon electrode in 0.1 M TEAP as supporting electrolyte solutidn.

DMF 용매에서 산소 첨가된 네자리 Schiff base cobalt(III)의 균일 촉매에 의하여 2,6-di-tert-butylphenol의 산화 주생성물인 2,6-ditert-butylbenzoquinone (BQ)일 때에는 O$_2$/Co몰 결합비가 1:1인 superoxo cobalt(III) 착물 곧 [Co(III)(Schiff base)(L)]$O_2$ (Schiff base; SED, SOPD and o-BSDT, L; DMF and Py)들의 활성촉매에 의하여 생긴다. 또, 산화생성물인 3,3',5,5'-tetra-tert-butyldiphenoquinone (DPQ)은 $O_2$/Co의 몰비가 1:2인 $\mu$-peroxo cobalt(III) 착물인 [Co(III)(SND)(L)]$_2$O$_2$ (L; DMF 및 Py)의 활성촉매에 의하여 생성된다. 이들 균일 활성촉매인 superoxo 및 $\mu$-peroxo cobalt(III) 착물들의 확인은 DMF나 DMSO 용매에서는 어렵다. 그러나 pyridine 용매에서는 산소흡착에 의한 PVT 법과 0.1 M TEAP의 지지전해질과 유리질 탄소전극을 사용한 순환 전압전류법으로 1:1 oxygen adduct인 superoxo 착물들은 $O_2$-의 prewave가 없는 3단계 환원과정으로만 일어나는 것으로 확인할 수 있었다.

Keywords

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