Issue 6, 2010

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

Abstract

The reaction of the iron(II) complex supported by the ligand L52aH (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) FeIII(OOH) complex. This reaction, where the anion BPh4 acts as an electron donor, is reminiscent of the reductive activation of O2 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.

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

Supplementary files

Article information

Article type
Paper
Submitted
02 Sep 2009
Accepted
29 Oct 2009
First published
15 Dec 2009

Dalton Trans., 2010,39, 1630-1634

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

M. Martinho, G. Blain and F. Banse, Dalton Trans., 2010, 39, 1630 DOI: 10.1039/B918061C

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