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

作者：Walleck, Stephan; Zimmermann, Thomas Philipp; Hachmeister, Henning; Pilger, Christian; Huser, Thomas; Katz, Sagie; Hildebrandt, Peter; Stammler, Anja; Bögge, Hartmut; Bill, Eckhard; Glaser, Thorsten^*

来源：Nature Communications, 2022, 13(1): 1376.

DOI：10.1038/s41467-022-28894-5

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.

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