Defluorination of Fluorophenols by a Nonheme Iron(IV)‐Oxo Species: Observation of a New Intermediate Along the Reaction
High‐valent iron(IV)‐oxo intermediates are versatile oxidants in the biotransformation of various substrates by metalloenzymes and catalyze essential reactions for human health as well as in the biodegradation of toxic organic pollutants in the environment. Herein, we report a biomimetic system that...
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Veröffentlicht in: | Chemistry : a European journal 2023-07, Vol.29 (39), p.e202300478-n/a |
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Sprache: | eng |
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Zusammenfassung: | High‐valent iron(IV)‐oxo intermediates are versatile oxidants in the biotransformation of various substrates by metalloenzymes and catalyze essential reactions for human health as well as in the biodegradation of toxic organic pollutants in the environment. Herein, we report a biomimetic system that efficiently reacts with halophenols through defluorination reactions and characterize various short‐lived intermediates along the reaction mechanism. We study the reactivity pattern of a nonheme iron(IV)‐oxo species with a series of trihalophenols (X=F, Cl, Br). A combined experimental and computational study reveals that the oxidative dehalogenation of 2,4,6‐trifluorophenol is initiated with an H‐atom ion from the phenolic group by the iron(IV)‐oxo species resulting in the formation of a phenolate radical and an iron(III)‐hydroxo species. This iron(III)‐hydroxo species forms an adduct with the oxidized substrate with λmax at 558 nm which subsequently decays to give quinones as products.
A combined experimental and computational study on a biomimetic iron(IV)‐oxo species in reaction with halophenols gives efficient dehalogenation including defluorination in the product. Along the reaction mechanism a novel intermediate is characterized spectroscopically and assigned to be an iron(III)‐hydroxo adduct. |
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ISSN: | 0947-6539 1521-3765 |
DOI: | 10.1002/chem.202300478 |