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Generation of a μ-1,2-hydroperoxo Fe(III)Fe(III) and a μ-1,2-peroxo Fe(IV)Fe(III) Complex

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 no...

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Detalles Bibliográficos
Autores principales: Walleck, Stephan, Zimmermann, Thomas Philipp, Hachmeister, Henning, Pilger, Christian, Huser, Thomas, Katz, Sagie, Hildebrandt, Peter, Stammler, Anja, Bögge, Hartmut, Bill, Eckhard, Glaser, Thorsten
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8927127/
https://www.ncbi.nlm.nih.gov/pubmed/35296656
http://dx.doi.org/10.1038/s41467-022-28894-5
Descripción
Sumario: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 {Fe(III)(μ-O)(μ-1,2-O(2))Fe(III)} 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 Fe(IV)Fe(III) 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.