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Main Title: O−O Bond Formation and Liberation of Dioxygen Mediated by N5‐Coordinate Non‐Heme Iron(IV) Complexes
Author(s): Kroll, Nicole
Speckmann, Ina
Schoknecht, Marc
Gülzow, Jana
Diekmann, Marek
Pfrommer, Johannes
Stritt, Anika
Schlangen, Maria
Grohmann, Andreas
Hörner, Gerald
Type: Article
Language Code: en
Abstract: 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, N5‐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 [FeIV(O)] and [FeV(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.
Issue Date: 13-Aug-2019
Date Available: 13-Feb-2020
DDC Class: 540 Chemie und zugeordnete Wissenschaften
Subject(s): bioinorganic chemistry
nitrogen ligands
O−O activation
oxo ligands
Sponsor/Funder: DFG, 12489635, SFB 658: Elementarprozesse in molekularen Schaltern auf Oberflächen
TU Berlin, Open-Access-Mittel - 2019
Journal Title: Angewandte Chemie International Edition
Publisher: Wiley
Publisher Place: Weinheim
Volume: 58
Issue: 38
Publisher DOI: 10.1002/anie.201903902
Page Start: 13472
Page End: 13478
EISSN: 1521-3773
ISSN: 1433-7851
Appears in Collections:FG Bioanorganische Chemie » Publications

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