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
收藏
页码：1630 / 1634
页数：5
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