Author Archives: Draksharapu A, Angelone D, Quesne MG, Padamati SK, Gómez L, Hage R, Costas M, Browne WR, de Visser SP

Identification and Spectroscopic Characterization of Nonheme Iron(III) Hypochlorite Intermediates.

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Identification and Spectroscopic Characterization of Nonheme Iron(III) Hypochlorite Intermediates.

Angew Chem Int Ed Engl. 2015 Feb 6;

Authors: Draksharapu A, Angelone D, Quesne MG, Padamati SK, Gómez L, Hage R, Costas M, Browne WR, de Visser SP

Abstract
Fe(III) -hypohalite complexes have been implicated in a wide range of important enzyme-catalyzed halogenation reactions including the biosynthesis of natural products and antibiotics and post-translational modification of proteins. The absence of spectroscopic data on such species precludes their identification. Herein, we report the generation and spectroscopic characterization of nonheme Fe(III) -hypohalite intermediates of possible relevance to iron halogenases. We show that Fe(III) -OCl polypyridylamine complexes can be sufficiently stable at room temperature to be characterized by UV/Vis absorption, resonance Raman and EPR spectroscopies, and cryo-ESIMS. DFT methods rationalize the pathways to the formation of the Fe(III) -OCl, and ultimately Fe(IV) O, species and provide indirect evidence for a short-lived Fe(II) -OCl intermediate. The species observed and the pathways involved offer insight into and, importantly, a spectroscopic database for the investigation of iron halogenases.

PMID: 25663379 [PubMed – as supplied by publisher]

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