Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 58, Issue 38, Pages 13472-13478Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201903902
Keywords
bioinorganic chemistry; iron; nitrogen ligands; O-O activation; oxo ligands
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Funding
- Deutsche Forschungsgemeinschaft (DFG) [GR 1247/7-1, SFB 658]
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Formation of the O-O bond is considered the critical step in oxidative water cleavage to produce dioxygen. High-valent metal complexes with terminal oxo (oxido) ligands are commonly regarded as instrumental for oxygen evolution, but direct experimental evidence is lacking. Herein, we describe the formation of the O-O bond in solution, from non-heme, N-5-coordinate oxoiron(IV) species. Oxygen evolution from oxoiron(IV) is instantaneous once meta-chloroperbenzoic acid is administered in excess. Oxygen-isotope labeling reveals two sources of dioxygen, pointing to mechanistic branching between HAT (hydrogen atom transfer)-initiated free-radical pathways of the peroxides, which are typical of catalase-like reactivity, and iron-borne O-O coupling, which is unprecedented for non-heme/peroxide systems. Interpretation in terms of [Fe-IV(O)] and [Fe-V(O)] being the resting and active principles of the O-O coupling, respectively, concurs with fundamental mechanistic ideas of (electro-) chemical O-O coupling in water oxidation catalysis (WOC), indicating that central mechanistic motifs of WOC can be mimicked in a catalase/peroxidase setting.
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