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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 37, Number 7
JKCSEZ 37(7)
February 20, 1993 

Saturated- and Unsaturated-Azamacrocyclic Complexes (M = Co3+, Fe3+ and Mn3+) Catalyzed Oxidation of Hindered Phenols by Molecular Oxygen under Sodium Borohydride

Sodium Borohydride 하에서 산소에 의한 포화- 및 불포화-질소주게 거대고리 착물 (M = Co3+, Fe3+ 및 Mn3+)을 촉매로 한 Hindered Phenols의 산화반응
Yu-Chul Park, Seong-Su Kim, Hun-Gil Na

박유철, 김성수, 나훈길
[M(cyclam)X2]Y(M = Co3+, Fe3+, Mn3+ : X = Cl-, Br-, NCS- : Y = Cl-, Br-, NCS-), [Co(trans-14-diene)X2]Y(X = Cl-, Br- : Y = ClO4-) 및 [Co(trans-14-diene)](ClO4)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)X2]Y은 불포화 거대고리착물 [Co(trans-14-diene)X2]Y에 비하여 더 효과적인 촉매제이었다. 촉매로 작용한 Co(Ⅲ)-거대고리착물과 산소간의 몰 결합비(O2/M)는 1/1이었고, [M(cyclam)Cl2]Cl(M = Fe(Ⅲ), Mn(Ⅲ))에서는 이들 비가 1/2이었다. 반응(10)과 (2)에서 산소분자의 활성종은 Co(Ⅲ) 거대고리착물이온과 [M(cyclam)Cl2]Cl(M = Fe(Ⅲ), Mn(Ⅲ))에서 각각 superoxolike(O2)와 peroxolike(O22-)로 가정하였다.

[M(cyclam)X2]Y(M = Co3+, Fe3+, Mn3+ : X = Cl-, Br-, NCS- : Y = Cl-, Br-, NCS-), [Co(trans-14-diene)X2]Y(X = Cl-, Br- : Y = ClO4-) and [Co(trans-14-diene)](ClO4)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)X2]Y, were more an effective catalyst than [Co(trans-14-diene)X2]Y the unsaturated complexes in the formation of BQ and DPQ. The mole ratio of O2 vs. catalyst (O2/M) for [Co(cyclam)X2]Y and [Co(trans-14-diene)X2]Y was 1/1, while it was 1/2 for [M(cyclam)Cl2]Cl(M = Fe(Ⅲ), Mn(Ⅲ)). The results suggested that Co(Ⅲ)-macrocyclic complexes activated molecular oxygen as superoxolike O2-and [M(cyclam)Cl2]Cl(M = Fe(Ⅲ), Mn(Ⅲ)) activated that as peroxolike O22-.

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