Generation of a μ-1,2-hydroperoxo FeIIIFeIII and a μ-1,2-peroxo FeIVFeIII Complex

Stephan Walleck, Thomas Philipp Zimmermann, Henning Hachmeister, Christian Pilger, Thomas Huser, Sagie Katz, Peter Hildebrandt, Anja Stammler, Hartmut Bögge, Eckhard Bill and Thorsten Glaser ()
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Stephan Walleck: Lehrstuhl für Anorganische Chemie I, Fakultät für Chemie, Universität Bielefeld, Universitätsstr. 25
Thomas Philipp Zimmermann: Lehrstuhl für Anorganische Chemie I, Fakultät für Chemie, Universität Bielefeld, Universitätsstr. 25
Henning Hachmeister: Biomolekulare Photonik, Fakultät für Physik, Universität Bielefeld, Universitätsstr. 25
Christian Pilger: Biomolekulare Photonik, Fakultät für Physik, Universität Bielefeld, Universitätsstr. 25
Thomas Huser: Biomolekulare Photonik, Fakultät für Physik, Universität Bielefeld, Universitätsstr. 25
Sagie Katz: Institut für Chemie, Technische Universität Berlin
Peter Hildebrandt: Institut für Chemie, Technische Universität Berlin
Anja Stammler: Lehrstuhl für Anorganische Chemie I, Fakultät für Chemie, Universität Bielefeld, Universitätsstr. 25
Hartmut Bögge: Lehrstuhl für Anorganische Chemie I, Fakultät für Chemie, Universität Bielefeld, Universitätsstr. 25
Eckhard Bill: Max-Planck-Institut für Chemische Energiekonversion
Thorsten Glaser: Lehrstuhl für Anorganische Chemie I, Fakultät für Chemie, Universität Bielefeld, Universitätsstr. 25

Nature Communications, 2022, vol. 13, issue 1, 1-11

Abstract: Abstract μ-1,2-Peroxo-diferric intermediates (P) of non-heme diiron enzymes are proposed to convert upon protonation either to high-valent active species or to activated P′ intermediates via hydroperoxo-diferric intermediates. Protonation of synthetic μ-1,2-peroxo model complexes occurred at the μ-oxo and not at the μ-1,2-peroxo bridge. Here we report a stable μ-1,2-peroxo complex {FeIII(μ-O)(μ-1,2-O2)FeIII} using a dinucleating ligand and study its reactivity. The reversible oxidation and protonation of the μ-1,2-peroxo-diferric complex provide μ-1,2-peroxo FeIVFeIII and μ-1,2-hydroperoxo-diferric species, respectively. Neither the oxidation nor the protonation induces a strong electrophilic reactivity. Hence, the observed intramolecular C-H hydroxylation of preorganized methyl groups of the parent μ-1,2-peroxo-diferric complex should occur via conversion to a more electrophilic high-valent species. The thorough characterization of these species provides structure-spectroscopy correlations allowing insights into the formation and reactivities of hydroperoxo intermediates in diiron enzymes and their conversion to activated P′ or high-valent intermediates.

Date: 2022
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DOI: 10.1038/s41467-022-28894-5

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