Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Oxidation Reaction of Hydrazobenzene by Activated Catalysts of Oxygen Adducted Tetradentate Schiff Base Cobalt(Ⅱ) Complexes in Methanol Solvent. (Ⅱ)

메탄올 용매에서 산소 첨가된 네자리 Schiff Base Cobalt(II) 착물들의 활성촉매에 의한 Hydrazobenzene의 산화반응 (제 2 보)

  • Ki-Kyung Chjo (Department of Chemistry, College of Natural Science, Chonnam National University) ;
  • Yong-Kook Choi (Department of Chemistry, College of Natural Science, Chonnam National University) ;
  • Sang-Bock Kim (Department of Chemistry, University of Ulsan) ;
  • Jong-Ki Park (Department of Chemistry, College of Natural Science, Chonnam National University) ;
  • Dong-Hwa Park (Department of Chemistry, College of Natural Science, Chonnam National University)
  • 조기형 (전남대학교 자연과학대학 화학과) ;
  • 최용국 (전남대학교 자연과학대학 화학과) ;
  • 김상복 (울산대학교 자연과학대학 화학과) ;
  • 박종기 (전남대학교 자연과학대학 화학과) ;
  • 박동화 (전남대학교 자연과학대학 화학과)
  • Published : 1992.12.20
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Abstract

Dioxygen binding and homogeneous catalytic oxidation of hydrazobenzene were investigated by employing tetradentate Schiff base Cobalt(II) complexes such as Co(II)(SED)$(Py)_2$, Co(II)(SOPD)$(Py)_2$ and Co(II)(SND)$(Py)_2$ in saturated oxygen methanol solvent. The major product of hydrazobenzene ($H_2$AB) oxidation by catalysts of superoxo type [Co(III)(SED)(Py)$O_2$] and [Co(III)(SOPD)(Py)$O_2$] complexes are trans-azobenzene (t-AB) and rate constants k for oxidation reaction was 7.692 ${\times}$ $10^{-2}$ M/sec for [Co(III)(SED)(Py)$O_2$] and 5.076 ${\times}$ $10^{-2}$ M/sec for [Co(III)(SOPD)(Py)$O_2$]. But cis-azobenzene (c-AB) are obtained as a major product with ${\mu}$-peroxo type [Co(III)(SED)(Py)]$_2O_2$ catalyst, and rate constant k is 1.266 ${\times}$ $10^{-2}$ M/sec. The rate constants of oxidation reaction has been studied spectrophotometrically and the rate law established. A mechanism involving a intermediate activated complexes of catalyst, hydrazobenzene and oxygen has been proposed. $H_2$AB + Co(II)(Schiff base)$(Py)_2$ + $O_2$ ${\rightleftharpoons}_{MeOH}^K$ Co(III)(Schiff base)(Py)$O_2$${\cdot}$$H_2$AB + Py $\longrightarrow^k$ Co(II)(Schiff base)$(Py)_2$ + t-AB + $H_2O_2$(Scchiff base : SED and SOPD). $H_2$AB + 2Co(II)(SND)$(Py)_2$ + $O_2$ ${\rightleftharpoons}_{MeOH}^K$ [Co(III)(SND)(Py)]$_2O_2$${\cdot}$H_2$AB + 2Py ${\longrightarrow}^k$ (Co(II)(SND)$(Py)_2$ + c-AB + $H_2O_2$.

산소가 포화된 메탈올 용액에서 Superoxo형인 [Co(Ⅲ)(SED)(Py)$O_2$]와 [Co(III)(SOPD)(Py)$O_2$]들의 균일 산화 활성 촉매에 의한 hydrazobenzene(H2AB)의 산화 주생성물은 trans-azobenzene (t-AB)이고 반응 속도상수 k = 7.692 ${\times}$ $10^{-2}$ M/sec 및 5.076 ${\times}$ $10^{-2}$ M/sec이나 ${\mu}$-peroxo형인 [Co(III)(SED)(Py)]$_2O_2$에 의한 주생성물은 cis-azobenzene (c-AB)이 선택적으로 생성되고 반은 속도상수 k = 1.266 ${\times}$ $10^{-2}$ M/sec로 주어짐을 UV-visible 흡광도법으로 알아보았다. 이들 산화반응은 다음과 같이 균일 산소 첨가 착물촉매에 의하여 산화주생성물이 선택적으로 다르게 생성된다. $H_2$AB + Co(II)(Schiff base)$(Py)_2$ + $O_2$ ${\rightleftharpoons}_{MeOH}^K$ Co(III)(Schiff base)(Py)$O_2$${\cdot}$$H_2$AB + Py $\longrightarrow^k$ Co(II)(Schiff base)$(Py)_2$ + t-AB + $H_2O_2$(Scchiff base : SED 및 SOPD). $H_2$AB + 2Co(II)(SND)$(Py)_2$ + $O_2$ ${\rightleftharpoons}_{MeOH}^K$ [Co(III)(SND)(Py)]$_2O_2$${\cdot}$$H_2$AB + 2Py $\longrightarrow^k$ (Co(II)(SND)$(Py)_2$ + c-AB + $H_2O_2$.

Keywords

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