Identification and spectroscopic characterization of nonheme iron(III) hypochlorite intermediates

Apparao Draksharapu, Davide Angelone, Matthew G. Quesne, Sandeep K. Padamati, Laura Gõmez, Ronald Hage, Miquel Costas, Wesley R. Browne, Sam P. De Visser

Research output: Contribution to journalArticlepeer-review

27 Scopus citations

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.

Original languageEnglish (US)
Pages (from-to)4357-4361
Number of pages5
JournalAngewandte Chemie - International Edition
Volume54
Issue number14
DOIs
StatePublished - Mar 27 2015

Bibliographical note

Publisher Copyright:
© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Keywords

  • EPR spectroscopy
  • Raman spectroscopy
  • hypochlorite
  • iron
  • metalloenzymes

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