Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Saturated- and Unsaturated-Azamacrocyclic Complexes $(M = Co^{3+}, Fe^{3+}$ or $Mn^{3+})$ Catalyzed Oxidation of Hindered Phenols by Molecular Oxygen under Sodium Borohydride

Sodium Borohydride 하에서 산소에 의한 포화- 및 불포화-질소주게 거대고리 착물 $(M=Co^{3+},\;Fe^{3+}$ 및 $Mn^{3+})$을 촉매로 한 Hindered Phenols의 산화반응

  • Yu-Chul Park (Department of Chemistry, Kyungpook National University) ;
  • Seong-Su Kim (Department of Chemistry, Kyungpook National University) ;
  • Hun-Gil Na (Department of Chemistry, Kyungpook National University)
  • 박유철 (경북대학교 자연과학대학 화학과) ;
  • 김성수 (경북대학교 자연과학대학 화학과) ;
  • 나훈길 (경북대학교 자연과학대학 화학과)
  • Published : 1993.07.20
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Abstract

$[M(cyclam)X_2]Y(M=Co^{3+},\;Fe^{3+},\;Mn^{3+}\;:\;X=Cl-^,\;Br^-,\;NCS^-\;:\;Y=Cl^-,\;Br^-,\;NCS^-),\;[Co(trans-14-diene)X_2]Y(X=Cl^-,\;Br^-\;:\;Y=ClO_4^-)\;and\;[Co(trans-14-diene)](ClO_4)_2$ were able to activate an molecular oxygen under sodium borohydride. 2,4-di-tert-butylphenol and 2,6-di-tert-butylphenol reacted with activated molecular oxygen to give 2,4-tert-butyl-1,6-benzoquinone(BQ) and 3,5,3',5'-tetra-tert-butyldiphenoquinone(DPQ). The saturated tetraazamacrocyclic complexes, $[Co(cyclam)X_2]Y$, were more an effective catalyst than $[Co(trans-14-diene)X_2]Y$ the unsaturated complexes in the formation of BQ and DPQ. The mole ratio of $O_2$ vs. catalyst $(O_2/M)$ for $[Co(cyclam)X_2]Y$ and [Co(trans-14-diene)X_2]Y$ was 1/1, while it was 1/2 for $[M(cyclam)Cl_2]Cl(M=Fe(III),\;Mn(III))$. The results suggested that Co(III)-macrocyclic complexes activated molecular oxygen as superoxolike ${O_2}^-$ and $[M(cyclam)Cl_2]Cl(M=Fe(III),\;Mn(III))$ activated that as peroxolike $O_2^{2-}$.

$[M(cyclam)X_2]Y(M=Co^{3+},\;Fe^{3+},\;Mn^{3+}\;:\;X=Cl-^,\;Br^-,\;NCS^-\;:\;Y=Cl^-,\;Br^-,\;NCS^-),\;[Co(trans-14-diene)X_2]Y(X=Cl^-,\;Br^-\;:\;Y= ClO_4^-)$ 및 $[Co(trans-14-diene)](ClO_4)_2$ 착이온은 sodium borohydride 하에서 산소를 활성화시킬 수 있었다. 활성화된 산소에 의한 2,4-di-tert-butylphenol 과 2,6-di-tert-butylphenol 산화반응의 생성물질을 각각 2,4-tert-butyl-1,6-benzoquinone(BQ) 와 3,5,3',5'-tetra-tert-butyldiphenoquinone(DPQ) 이었다. BQ와 DPQ 생성반응에서 포화 거대고리 리간드 착물인 $[Co(cyclam)X_2]Y$은 불포화 거대고리착물 $[Co(trans-14-diene)X_2]Y$에 비하여 더 효과적인 촉매제이었다. 촉매로 작용한 Co(III)-거대고리착물과 산소간의 몰 결합비$(O_2/M)$는 1/1이었고, $[M(cyclam)Cl_2]Cl(M=Fe(III)$, Mn(III))에서는 이들 비가 1/2이었다. 반응(10)과 (2)에서 산소분자의 활성종은 Co(III) 거대고리착물이온과 $[M(cyclam)Cl_2]Cl(M=Fe(III)$, Mn(III))에서 각각 superoxolike$({O_2}^-)$와 peroxolike$({O_2}^{2-})$로 가정하였다.

Keywords

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