A Synthetic Model of the Putative Fe(II)-Iminobenzosemiquinonate Intermediate in the Catalytic Cycle of o-Aminophenol Dioxygenases

被引：36

作者：

Bittner, Michael M. ^{[1
]}

Lindeman, Sergey V. ^{[1
]}

Fiedler, Adam T. ^{[1
]}

机构：

[1] Marquette Univ, Dept Chem, Milwaukee, WI 53201 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2012年 / 134卷 / 12期

基金：

美国国家科学基金会;

关键词：

2-HIS-1-CARBOXYLATE FACIAL TRIAD; RING-CLEAVING DIOXYGENASES; CATECHOL DIOXYGENASES; EXTRADIOL DIOXYGENASES; ELECTRONIC-STRUCTURE; FUNCTIONAL MODELS; COMPLEXES; LIGANDS; MECHANISM; IRON(III);

D O I：

10.1021/ja212163t

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The oxidative ring cleavage of aromatic substrates by nonheme Fe dioxygenases is thought to involve formation of a ferrous-(substrateradical) intermediate. Here we describe the synthesis of the trigonal-bipyramdial complex Fe((Ph2)Tp)(ISQ(tBU)) (2), the first synthetic example of an iron(II) center bound to an iminobenzosemiquinonate (ISQ) radical. The unique electronic structure of this S = 3/2 complex and its one-electron oxidized derivative ([3](+)) have been established on the basis of crystallographic, spectroscopic, and computational analyses. These findings further demonstrate the viability of Fe2+-ISQ intermediates in the catalytic cycles of o-aminophenol dioxygenases.

引用

页码：5460 / 5463

页数：4

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