Abstract
An isotopically enriched [57Fe(edta)(O2)]3− complex, formed by the addition of H2O2 to a 57FeIII-edta (edta = ethylenediaminetetraacetic acid) complex at elevated pH (pH = 11.3), was studied by Mossbauer spectroscopy. All Mossbauer parameters were determined for this nonheme high-spin ferric peroxo complex with an η2-FeO2 (side-on) arrangement by a numerical treatment of applied field Mossbauer data. The peroxo complex exhibits an isomer shift δ/Fe = 0.65(1) mm s−1 and a quadrupole splitting ΔEQ = +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 [FeIII(N4Py)(η2-OO)]+ (Py = pyridine) [V. Vrajmasu, E. Munck, R. Ho, L. Que, Jr., G. Roefles, B. L. Feringa, J. Inorg. Biochem.2001, 86, 472]. The set of Mossbauer 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)
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