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

ABSTRACT: FeIII-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 FeIII-hypohalite intermediates of possible relevance to iron halogenases. We show that FeIII-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 FeIII-OCl, and ultimately FeIV=O, species and provide indirect evidence for a short-lived FeII-OCl intermediate. The species observed and the pathways involved offer insight into and, importantly, a spectroscopic database for the investigation of iron halogenases.

SUBMITTER: Draksharapu A 

PROVIDER: S-EPMC4955228 | biostudies-literature | 2015 Mar

REPOSITORIES: biostudies-literature

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

Draksharapu Apparao A   Angelone Davide D   Quesne Matthew G MG   Padamati Sandeep K SK   Gómez Laura L   Hage Ronald R   Costas Miquel M   Browne Wesley R WR   de Visser Sam P SP  

Angewandte Chemie (Weinheim an der Bergstrasse, Germany) 20150206 14

Fe<sup>III</sup>-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<sup>III</sup>-hypohalite intermediates of possible relevance to iron halogenases. We show that F  ...[more]

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