Bis-benzimidazolyl diamide copper (II) complexes: Synthesis, crystal structure and oxidation of substituted amino phenols

Bis-benzimidazolyl diamide copper (II) complexes: Synthesis, crystal structure and oxidation of substituted amino phenols
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DOI:
10.1016/j.inoche.2011.12.011
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发表时间:
2012-03-01
影响因子:
3.8
通讯作者:
Mathur, Pavan
Mathur, Pavan
中科院分区:
化学4区
文献类型:
--
作者:
Ahuja, Gauri;Mathur, Pavan

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利用一种新的四齿配体N,N '-二(1-丁基苯并咪唑-2-基甲基)己烷-1,6-二甲酰胺(b-GBSA)合成了内球阴离子配体NO3-、Br-和Cl-的单核铜(II)配合物。对其中两个配合物[Cu(L)NO_3] NO_3(1)和[Cu(L)Br]Br(2)进行了结构表征。在(1)中,Cu(II)的几何构型为畸变八面体,NO3-为双齿配体,而在(2)中,Cu(II)的几何构型为近四方锥。该配合物在分子氧存在下进行取代的氨基酚的氧化。2-氨基-5-甲基苯酚的氧化在二氢吩恶嗪酮阶段被阻断,2-氨基-4-叔丁基苯酚的氧化在邻醌阶段被阻断,非常像吩恶嗪酮合酶。(c)2011 Elsevier B. V.保留所有权利。
A new tetradentate ligand N,N'-Bis (1-butyl-benzimidazol-2-yl-methyl)-hexane-1,6-dicarboxamide (b-GBSA) has been utilized to synthesize mononuclear copper (II) complexes with inner sphere anionic ligands like NO3-, Br- and Cl-. Two of the complexes [Cu(L)NO3]NO3 (1) and [Cu(L)Br]Br (2) have been structurally characterized. The geometry of copper (II) in (1) is a distorted octahedral with NO3- anion acting as a bidentate ligand, while for (2) the geometry is found to be a near square pyramidal. The complexes carry out the oxidation of substituted amino phenols in the presence of molecular oxygen. The oxidation gets blocked at the dihydrophenoxazinone stage for 2-amino-5-methyl phenol, and to o-quinone for 2-amino-4-tertiary butyl phenol, quite like the enzyme phenoxazinone synthase. (c) 2011 Elsevier B.V. All rights reserved.