An Iron(III) Superoxide Corrole from Iron(II) and Dioxygen
Jireh Joy D. Sacramento, Therese Albert, Maxime A. Siegler, Pierre Moënne‐Loccoz, David P. Goldberg
Abstract
Abstract A new structurally characterized ferrous corrole [Fe II (ttppc)] − ( 1 ) binds one equivalent of dioxygen to form [Fe III (O 2 −. )(ttppc)] − ( 2 ). This complex exhibits a 16/18 O 2 ‐isotope sensitive ν(O‐O) stretch at 1128 cm −1 concomitantly with a single ν(Fe‐O 2 ) at 555 cm −1 , indicating it is an η 1 ‐superoxo (“end‐on”) iron(III) complex. Complex 2 is the first well characterized Fe‐O 2 corrole, and mediates the following biologically relevant oxidation reactions: dioxygenation of an indole derivative, and H‐atom abstraction from an activated O−H bond.
Topics & Concepts
CorroleChemistryFerrousPhotochemistryIndole testSuperoxideStereochemistryMedicinal chemistryOrganic chemistryEnzymeMetal-Catalyzed Oxygenation MechanismsPorphyrin and Phthalocyanine ChemistryHeme Oxygenase-1 and Carbon Monoxide