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

Walleck S, Zimmermann TP, Hachmeister H, Pilger C, Huser T, Katz S, Hildebrandt P, Stammler A, Bögge H, Bill E, Glaser T (2022)
Nature Communications 13(1): 1376.

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Abstract / Bemerkung
mu-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 mu-1,2-peroxo model complexes occurred at the mu-oxo and not at the mu-1,2-peroxo bridge. Here we report a stable mu-1,2-peroxo complex {FeIII(mu-O)(mu-1,2-O2)FeIII} using a dinucleating ligand and study its reactivity. The reversible oxidation and protonation of the mu-1,2-peroxo-diferric complex provide mu-1,2-peroxo FeIVFeIII and mu-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 mu-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. © 2022. The Author(s).
Erscheinungsjahr
2022
Zeitschriftentitel
Nature Communications
Band
13
Ausgabe
1
Art.-Nr.
1376
eISSN
2041-1723
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Open-Access-Publikationskosten wurden durch die Universität Bielefeld im Rahmen des DEAL-Vertrags gefördert.
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https://pub.uni-bielefeld.de/record/2962028

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Walleck S, Zimmermann TP, Hachmeister H, et al. Generation of a mu-1,2-hydroperoxo FeIIIFeIII and a mu-1,2-peroxo FeIVFeIII Complex. Nature Communications . 2022;13(1): 1376.
Walleck, S., Zimmermann, T. P., Hachmeister, H., Pilger, C., Huser, T., Katz, S., Hildebrandt, P., et al. (2022). Generation of a mu-1,2-hydroperoxo FeIIIFeIII and a mu-1,2-peroxo FeIVFeIII Complex. Nature Communications , 13(1), 1376. https://doi.org/10.1038/s41467-022-28894-5
Walleck, Stephan, Zimmermann, Thomas Philipp, Hachmeister, Henning, Pilger, Christian, Huser, Thomas, Katz, Sagie, Hildebrandt, Peter, et al. 2022. “Generation of a mu-1,2-hydroperoxo FeIIIFeIII and a mu-1,2-peroxo FeIVFeIII Complex”. Nature Communications 13 (1): 1376.
Walleck, S., Zimmermann, T. P., Hachmeister, H., Pilger, C., Huser, T., Katz, S., Hildebrandt, P., Stammler, A., Bögge, H., Bill, E., et al. (2022). Generation of a mu-1,2-hydroperoxo FeIIIFeIII and a mu-1,2-peroxo FeIVFeIII Complex. Nature Communications 13:1376.
Walleck, S., et al., 2022. Generation of a mu-1,2-hydroperoxo FeIIIFeIII and a mu-1,2-peroxo FeIVFeIII Complex. Nature Communications , 13(1): 1376.
S. Walleck, et al., “Generation of a mu-1,2-hydroperoxo FeIIIFeIII and a mu-1,2-peroxo FeIVFeIII Complex”, Nature Communications , vol. 13, 2022, : 1376.
Walleck, S., Zimmermann, T.P., Hachmeister, H., Pilger, C., Huser, T., Katz, S., Hildebrandt, P., Stammler, A., Bögge, H., Bill, E., Glaser, T.: Generation of a mu-1,2-hydroperoxo FeIIIFeIII and a mu-1,2-peroxo FeIVFeIII Complex. Nature Communications . 13, : 1376 (2022).
Walleck, Stephan, Zimmermann, Thomas Philipp, Hachmeister, Henning, Pilger, Christian, Huser, Thomas, Katz, Sagie, Hildebrandt, Peter, Stammler, Anja, Bögge, Hartmut, Bill, Eckhard, and Glaser, Thorsten. “Generation of a mu-1,2-hydroperoxo FeIIIFeIII and a mu-1,2-peroxo FeIVFeIII Complex”. Nature Communications 13.1 (2022): 1376.
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