Volume 61, Issue 2 e202111492
Communication

An Iron(III) Superoxide Corrole from Iron(II) and Dioxygen

Jireh Joy D. Sacramento

Jireh Joy D. Sacramento

Department of Chemistry, The Johns Hopkins University, 3400 North Charles Street, Baltimore, MD, 21218 USA

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Therese Albert

Therese Albert

Department of Chemical Physiology and Biochemistry, Oregon Health & Science University, Portland, OR, 97239-3098 USA

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Maxime Siegler

Maxime Siegler

Department of Chemistry, The Johns Hopkins University, 3400 North Charles Street, Baltimore, MD, 21218 USA

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Pierre Moënne-Loccoz

Corresponding Author

Pierre Moënne-Loccoz

Department of Chemical Physiology and Biochemistry, Oregon Health & Science University, Portland, OR, 97239-3098 USA

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David P. Goldberg

Corresponding Author

David P. Goldberg

Department of Chemistry, The Johns Hopkins University, 3400 North Charles Street, Baltimore, MD, 21218 USA

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First published: 30 November 2021
Citations: 16

Graphical Abstract

An iron-superoxide corrole has been generated from a ferrous corrole and dioxygen, and was found to be capable of indole dioxygenation and H-atom transfer reactions.

Abstract

A new structurally characterized ferrous corrole [FeII(ttppc)] (1) binds one equivalent of dioxygen to form [FeIII(O2−.)(ttppc)] (2). This complex exhibits a 16/18O2-isotope sensitive ν(O-O) stretch at 1128 cm−1 concomitantly with a single ν(Fe-O2) at 555 cm−1, indicating it is an η1-superoxo (“end-on”) iron(III) complex. Complex 2 is the first well characterized Fe-O2 corrole, and mediates the following biologically relevant oxidation reactions: dioxygenation of an indole derivative, and H-atom abstraction from an activated O−H bond.

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