Conflicting Role of Water in the Activation of H2O2 and the Formation and Reactivity of Non-Heme Fe(III)-OOH and Fe(III)-O-Fe(III) Complexes at Room Temperature

The formation of an Fe(III)-OOH species by reaction of complex 1 ([(MeN3Py)Fe(II)(CH3CN)2](2+)) with H2O2 at room temperature is reported and is studied by a combination of UV/vis absorption, EPR, and resonance Raman spectroscopies. The formation of the Fe(III)-OOH species, and its subsequent conver...

Full description

Saved in:
Bibliographic Details
Published in:Inorganic chemistry 2016-05, Vol.55 (9), p.4211-4222
Main Authors: Padamati, Sandeep K, Draksharapu, Apparao, Unjaroen, Duenpen, Browne, Wesley R
Format: Article
Language:English
Subjects:
Acetic Acid - chemistry
Acetonitriles - chemistry
Alkenes - chemistry
Coordination Complexes - chemistry
Electrochemical Techniques
Hydrogen Peroxide - chemistry
Iron Compounds - chemistry
Kinetics
Ligands
Oxidation-Reduction
Temperature
Water - chemistry
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:The formation of an Fe(III)-OOH species by reaction of complex 1 ([(MeN3Py)Fe(II)(CH3CN)2](2+)) with H2O2 at room temperature is reported and is studied by a combination of UV/vis absorption, EPR, and resonance Raman spectroscopies. The formation of the Fe(III)-OOH species, and its subsequent conversion to relatively inert Fe(III)-O-Fe(III) species, is shown to be highly dependent on the concentration of water, with excess water favoring the formation of the latter species, which is studied by UV/vis absorption spectroelectrochemistry also. The presence of acetic acid increases the rate and extent of oxidation of 1 to its iron(III) state and inhibits the wasteful decomposition of H2O2 but does not affect significantly the spectroscopic properties of the Fe(III)-OOH species formed.
ISSN:1520-510X
DOI:10.1021/acs.inorgchem.5b02976