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

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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)

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.

Suggested Citation

  • Stephan Walleck & Thomas Philipp Zimmermann & Henning Hachmeister & Christian Pilger & Thomas Huser & Sagie Katz & Peter Hildebrandt & Anja Stammler & Hartmut Bögge & Eckhard Bill & Thorsten Glaser, 2022. "Generation of a μ-1,2-hydroperoxo FeIIIFeIII and a μ-1,2-peroxo FeIVFeIII Complex," Nature Communications, Nature, vol. 13(1), pages 1-11, December.
    • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-28894-5
    DOI: 10.1038/s41467-022-28894-5
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    References listed on IDEAS

    as
    1. Justin F. Acheson & Lucas J. Bailey & Thomas C. Brunold & Brian G. Fox, 2017. "In-crystal reaction cycle of a toluene-bound diiron hydroxylase," Nature, Nature, vol. 544(7649), pages 191-195, April.
    2. Rahul Banerjee & Yegor Proshlyakov & John D. Lipscomb & Denis A. Proshlyakov, 2015. "Structure of the key species in the enzymatic oxidation of methane to methanol," Nature, Nature, vol. 518(7539), pages 431-434, February.
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