Activation of dioxygen by a mononuclear non-heme iron complex: characterization of a FeIII(OOH) intermediate

被引：39

作者：

Martinho, Marlene ^{[1
]}

Blain, Guillaume ^{[1
]}

Banse, Frederic ^{[1
]}

机构：

[1] Univ Paris 11, Chim Inorgan Lab, Inst Chim Mol & Mat Orsay, F-91405 Orsay, France

来源：

DALTON TRANSACTIONS | 2010年 / 39卷 / 06期

关键词：

SPIN FE(IV) INTERMEDIATE; FE-III; SPECTROSCOPIC EVIDENCE; TETRAPHENYLBORATE ION; PENTADENTATE LIGAND; OXYGEN ACTIVATION; ELECTROOXIDATION; ABSTRACTION; REACTIVITY; BLEOMYCIN;

D O I：

10.1039/b918061c

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The reaction of the iron(II) complex supported by the ligand L(5)(2)aH (2,2-dimethyl-N-[6-({[2-(methyl-pyridin-2- ylmethyl-amino)-ethyl]-pyridin-2-ylmethyl-amino}-methyl)-pyridin-2-yl]-propionamide) with dioxygen, in the presence of HClO4 and NaBPh4 yields the corresponding low spin (S = 1/2) Fe-III(OOH) complex. This reaction, where the anion BPh4- acts as an electron donor, is reminiscent of the reductive activation of O-2 by enzymatic systems. Under these specific experimental conditions, the hydroperoxoiron(III) complex evolves in an unexpected way to yield a high spin (S = 5/2) green species. This transformation is shown to arise from the reaction between the hydroperoxoiron(III) intermediate and BPh3, a side product of BPh4-.

引用

页码：1630 / 1634

页数：5

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