N-O Bond Homolysis of an Iron(II) TEMPO Complex Yields an Iron(III) Oxo Intermediate

被引：53

作者：

Smith, Jeremy M. ^{[1
]}

Mayberry, Derick E. ^{[1
]}

Margaritt, Charles G. ^{[1
]}

Sutter, Joerg ^{[2
]}

Wang, Haobin ^{[1
]}

Meyer, Karsten ^{[2
]}

Bontchev, Ranko P. ^{[3
]}

机构：

[1] New Mexico State Univ, Dept Chem & Biochem, Las Cruces, NM 88003 USA

[2] Univ Erlangen Nurnberg, Dept Chem & Pharm, D-91058 Erlangen, Germany

[3] Cabot Corp, Albuquerque, NM 87113 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2012年 / 134卷 / 15期

关键词：

NONHEME OXOIRON(IV) COMPLEXES; ELECTRON-TRANSFER PROPERTIES; DIOXYGEN ACTIVATION; TRIVALENT CARBON; SPECTROSCOPIC EVIDENCE; CRYSTAL-STRUCTURE; HALOGENASE CYTC3; ATOM TRANSFER; TERMINAL OXO; REACTIVITY;

D O I：

10.1021/ja211882e

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The reaction of TEMPO with the iron(I) synthon PhB(MesIm)(3)Fe(COE) leads to formation of the kappa(1)-TEMPO complex PhB(MesIm)(3)Fe(TEMPO). Structural and spectroscopic data establish the complex contains divalent iron bound to a nitroxido anion and is isoelectronic to an iron(II) peroxo complex. Thermolysis of the complex results in N-O bond homolysis, leading to the formation of an iron(III) oxo intermediate. The oxo intermediate is active in oxygen atom transfer reactions and can be trapped by the triphenylmethyl radical to give the iron(II) alkoxo complex PhB(MesIm)(3)Fe(OCPh3).

引用

页码：6516 / 6519

页数：4

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