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A Mössbauer Study of [Fe(edta)(O 2 )] 3− Agrees with a High‐Spin Fe III Peroxo Complex
Author(s) -
Horner Olivier,
Jeandey Claudine,
Oddou JeanLouis,
Bonville Pierre,
Latour JeanMarc
Publication year - 2002
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200205)2002:5<1186::aid-ejic1186>3.0.co;2-x
Subject(s) - chemistry , mössbauer spectroscopy , ethylenediaminetetraacetic acid , pyridine , ferric , quadrupole splitting , chelation , crystallography , bioinorganic chemistry , inorganic chemistry , nuclear chemistry , stereochemistry , medicinal chemistry
An isotopically enriched [ 57 Fe(edta)(O 2 )] 3− complex, formed by the addition of H 2 O 2 to a 57 Fe III ‐edta (edta = ethylenediaminetetraacetic acid) complex at elevated pH (pH = 11.3), was studied by Mössbauer spectroscopy. All Mössbauer parameters were determined for this nonheme high‐spin ferric peroxo complex with an η 2 ‐FeO 2 (side‐on) arrangement by a numerical treatment of applied field Mössbauer data. The peroxo complex exhibits an isomer shift δ /Fe = 0.65(1) mm s −1 and a quadrupole splitting Δ E Q = +0.72(2) mm s −1 (T = 4.2 K). The isomer‐shift value is very similar to the value of δ /Fe = 0.61 mm s −1 published for the side‐on peroxo complex [Fe III (N 4 Py)(η 2 ‐OO)] + (Py = pyridine) [V. Vrajmasu, E. Münck, R. Ho, L. Que, Jr., G. Roefles, B. L. Feringa, J. Inorg. Biochem. 2001 , 86 , 472]. The set of Mössbauer parameters obtained herein is expected to aid the characterization of analogous species that may appear during dioxygen activation by nonheme mononuclear iron enzymes. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)