Electron paramagnetic resonance and Mössbauer spectroscopy and density functional theory analysis of a high-spin Fe(IV)-oxo complex.

Journal of the American Chemical Society
Rupal GuptaMichael P Hendrich

Abstract

High-spin Fe(IV)-oxo species are known to be kinetically competent oxidants in non-heme iron enzymes. The properties of these oxidants are not as well understood as the corresponding intermediate-spin oxidants of heme complexes. The present work gives a detailed characterization of the structurally similar complexes [Fe(IV)H(3)buea(O)](-), [Fe(III)H(3)buea(O)](2-), and [Fe(III)H(3)buea(OH)](-) (H(3)buea = tris[(N'-tert-butylureaylato)-N-ethylene]aminato) using Mössbauer and dual-frequency/dual-mode electron paramagnetic resonance (EPR) spectroscopies. The [Fe(IV)H(3)buea(O)](-) complex has a high-spin (S = 2) configuration imposed by the C(3)-symmetric ligand. The EPR spectra of the [Fe(IV)H(3)buea(O)](-) complex presented here represent the first documented examples of an EPR signal from an Fe(IV)-oxo complex, demonstrating the ability to detect and quantify Fe(IV) species with EPR spectroscopy. Quantitative simulations allowed the determination of the zero-field parameter, D = +4.7 cm(-1), and the species concentration. Density functional theory (DFT) calculations of the zero-field parameter were found to be in agreement with the experimental value and indicated that the major contribution to the D value is from spin-orbit co...Continue Reading

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Citations

Feb 26, 2013·Inorganic Chemistry·Matthew B ChambersDaniel G Nocera
Aug 22, 2012·Proceedings of the National Academy of Sciences of the United States of America·Martin SrnecEdward I Solomon
Jan 31, 2014·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Joshua TelserAndrew Ozarowski
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Sep 15, 2018·Chemistry : a European Journal·Pokhraj GhoshMichael B Hall
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Mar 12, 2020·Environmental Science & Technology·Sheng LiangChunhua Feng
Jun 4, 2020·Journal of the American Chemical Society·Victoria F OswaldA S Borovik
Jun 17, 2015·Biochemistry·Sarah A CookA S Borovik
Sep 21, 2016·Journal of the American Chemical Society·Ethan A HillA S Borovik
Nov 12, 2013·Journal of Chemical Theory and Computation·Mátyás Pápai, György Vankó
Jun 28, 2019·Journal of the American Chemical Society·Vishal YadavDavid P Goldberg
Jul 16, 2019·Inorganic Chemistry·Yoshihiro Shimoyama, Takahiko Kojima
Dec 29, 2020·Journal of the American Chemical Society·Vishal YadavDavid P Goldberg
Sep 8, 2021·Inorganic Chemistry·Justin L LeeA S Borovik

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