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O−O Bond Formation and Liberation of Dioxygen Mediated by N5‐Coordinate Non‐Heme Iron(IV) Complexes

Title data

Kroll, Nicole ; Speckmann, Ina ; Schoknecht, Marc ; Gülzow, Jana ; Diekmann, Marek ; Pfrommer, Johannes ; Stritt, Anika ; Schlangen, Maria ; Grohmann, Andreas ; Hörner, Gerald:
O−O Bond Formation and Liberation of Dioxygen Mediated by N5‐Coordinate Non‐Heme Iron(IV) Complexes.
In: Angewandte Chemie International Edition. Vol. 58 (16 September 2019) Issue 38 . - pp. 13472-13478.
ISSN 1521-3773
DOI: https://doi.org/10.1002/anie.201903902

Project information

Project financing: Deutsche Forschungsgemeinschaft

Abstract in another language

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.

Further data

Item Type: Article in a journal
Refereed: Yes
Institutions of the University: Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Inorganic Chemistry IV
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Inorganic Chemistry IV > Chair Inorganic Chemistry IV - Univ.-Prof. Dr. Birgit Weber
Faculties
Faculties > Faculty of Biology, Chemistry and Earth Sciences
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry
Result of work at the UBT: Yes
DDC Subjects: 500 Science > 540 Chemistry
Date Deposited: 29 Jun 2020 07:16
Last Modified: 02 Jul 2020 12:07
URI: https://eref.uni-bayreuth.de/id/eprint/55631