A dramatic push effect on the homolysis of FeIII(OOR) intermediates to form non-heme FeIV=O complexes

被引：77

作者：

Kaizer, J

Costas, M

Que, L

机构：

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

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

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2003年 / 42卷 / 31期

关键词：

high-valent species; iron; kinetics; oxo ligands; push effect;

D O I：

10.1002/anie.200351694

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A pushy Lewis base: Previously unobserved non-heme FeIV=O intermediates can be trapped in the decay of FeIIIOOR species by the addition of Lewis bases (represented by the green sphere) that promote O-O bond homolysis (see picture; Fe purple, O red).

引用

页码：3671 / 3673

页数：3

共 22 条

[1] THE REACTIVITY OF SPECTROSCOPICALLY DETECTED PEROXY COMPLEXES OF IRON PORPHYRINS [J].

BALCH, AL .

INORGANICA CHIMICA ACTA, 1992, 198 :297-307

[2] Biomimetic aryl hydroxylation derived from alkyl hydroperoxide at a nonheme iron center.: Evidence for an FeIV=O oxidant [J].

Jensen, MP ;

Lange, SJ ;

Mehn, MP ;

Que, EL ;

Que, L .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (08) :2113-2128

[3] Pterin-dependent amino acid hydroxylases [J].

Kappock, TJ ;

Caradonna, JP .

CHEMICAL REVIEWS, 1996, 96 (07) :2659-2756

[4] AN ALKYLPEROXOIRON(III) INTERMEDIATE AND ITS ROLE IN THE OXIDATION OF ALIPHATIC C-H BONDS [J].

KIM, J ;

LARKA, E ;

WILKINSON, EC ;

QUE, L .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1995, 34 (18) :2048-2051

[5]

Kim J., 1995, ANGEW CHEM, V107, P2191

[6] Electronic structure of high-spin iron(III)-alkylperoxo complexes and its relation to low-spin analogues: Reaction coordinate of O-O bond homolysis [J].

Lehnert, N ;

Ho, RYN ;

Que, L ;

Solomon, EI .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (51) :12802-12816

[7] Spectroscopic properties and electronic structure of low-spin Fe(III)-alkylperoxo complexes: Homolytic cleavage of the O-O bond [J].

Lehnert, N ;

Ho, RYN ;

Que, L ;

Solomon, EI .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (34) :8271-8290

[8] An FeIV=O complex of a tetradentate tripodal nonheme ligand [J].

Lim, MH ;

Rohde, JU ;

Stubna, A ;

Bukowski, MR ;

Costas, M ;

Ho, RYN ;

Münck, E ;

Nam, W ;

Que, L .

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2003, 100 (07) :3665-3670

[9] A putative monooxygenase mimic which functions via well-disguised free radical chemistry [J].

MacFaul, PA ;

Ingold, KU ;

Wayner, DDM ;

Que, L .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (44) :10594-10598

[10] Intermolecular trapping of a nonheme Fe(IV)=O intermediate [J].

Miyake, H ;

Chen, K ;

Lange, SJ ;

Que, L .

INORGANIC CHEMISTRY, 2001, 40 (14) :3534-3538

← 1 2 3 →