Volume profile analysis for the reversible binding of superoxide to form iron(II)-superoxo/iron(III)-Peroxo porphyrin complexes

Dürr KL, Jux N, Zahl A, van Eldik R, Ivanovic-Burmazovic I (2010)


Publication Type: Journal article, Original article

Publication year: 2010

Journal

Original Authors: Dürr K., Jux N., Zahl A., Van Eldik R., Ivanović-Burmazović I.

Publisher: American Chemical Society

Book Volume: 49

Pages Range: 11254-11260

Journal Issue: 23

DOI: 10.1021/ic102092h

Abstract

The one-electron reduced iron(II)-dioxygen adduct, {Fe-O }, is known to be an important intermediate in the catalytic cycle of heme (mono)oxygenases. The same type of species, considered as Fe-peroxo, can be formed in a direct reaction between a Fe center and superoxide. In a unique high-pressure study of the reaction between superoxide and the Fe complex of a crown ether porphyrin conjugate in dimethylsulfoxide (DMSO), the overall Fe -superoxide interaction mechanism could be visualized and the nature of all species that occur along the reaction coordinate could be clarified. The equilibrium between the low-spin and high-spin forms of the starting Fe complex was quantified, which turns out to be the actual activation step toward substitution and subsequent inner-sphere electron transfer reactions. The constructed reaction volume profile demonstrates that the reaction product consists of Fe-peroxo and Fe -superoxo species that exist in equilibrium, which can better account for the versatile reactivity of {Fe-O} adducts toward different substrates. © 2010 American Chemical Society.

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How to cite

APA:

Dürr, K.L., Jux, N., Zahl, A., van Eldik, R., & Ivanovic-Burmazovic, I. (2010). Volume profile analysis for the reversible binding of superoxide to form iron(II)-superoxo/iron(III)-Peroxo porphyrin complexes. Inorganic Chemistry, 49(23), 11254-11260. https://doi.org/10.1021/ic102092h

MLA:

Dürr, Katharina L., et al. "Volume profile analysis for the reversible binding of superoxide to form iron(II)-superoxo/iron(III)-Peroxo porphyrin complexes." Inorganic Chemistry 49.23 (2010): 11254-11260.

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