Sc3+-Triggered Oxoiron(IV) Formation from O2 and its Non-Heme Iron(II) Precursor via a Sc3+-Peroxo-Fe3+ Intermediate

被引：88

作者：

Li, Feifei ^{[1
,2
]}

Van Heuvelen, Katherine M. ^{[1
,2
]}

Meier, Katlyn K. ^{[3
]}

Muenck, Eckard ^{[3
]}

Que, Lawrence, Jr. ^{[1
,2
]}

机构：

[1] Univ Minnesota, Dept Chem, Minneapolis, MN 55455 USA

[2] Univ Minnesota, Ctr Met Biocatalysis, Minneapolis, MN 55455 USA

[3] Carnegie Mellon Univ, Dept Chem, Pittsburgh, PA 15213 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2013年 / 135卷 / 28期

基金：

美国国家科学基金会; 美国国家卫生研究院;

关键词：

COUPLED ELECTRON-TRANSFER; INACTIVE METAL-IONS; DIOXYGEN ACTIVATION; CRYSTAL-STRUCTURE; IRON(IV)-OXO COMPLEX; PEROXO COMPLEXES; HIGH-SPIN; REACTIVITY; PROTON; FE;

D O I：

10.1021/ja402645y

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We report that redox-inactive Sc3+ can trigger O-2 activation by the Fe-II(TMC) center (TMC = tetramethylcyclam) to generate the corresponding oxoiron(IV) complex in the presence of BPh4- as an electron donor. To model a possible intermediate in the above reaction, we generated an unprecedented Sc3+ adduct of [Fe-III(eta(2)-O-2)(TMC)](+) by an alternative route, which was found to have an Fe3+-(mu-eta(2):eta(2)-peroxo)-Sc3+ core and to convert to the oxoiron(IV) complex. These results have important implications for the role a Lewis acid can play in facilitating O-O bond deavage during the course of O-2 activation at non-heme iron centers.

引用

页码：10198 / 10201

页数：4

共 20 条

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Münck, E. (emunck@cmu.edu), 1600, American Chemical Society (135):
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ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2015, 249
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[8] Mechanistic Borderline of One-Step Hydrogen Atom Transfer versus Stepwise Sc3+-Coupled Electron Transfer from Benzyl Alcohol Derivatives to a Non-Heme Iron(IV)-Oxo Complex
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