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Reactivity of an FeIV-Oxo Complex with Protons and Oxidants

High-valent Fe-OH species are often invoked as key intermediates but have only been observed in Compound II of cytochrome P450s. To further address the properties of non-heme FeIV-OH complexes, we demonstrate the reversible protonation of a synthetic FeIV-oxo species containing a tris-urea tripodal ligand. The same protonated FeIV-oxo species can be prepared via oxidation, suggesting that a putative FeV-oxo species was initially generated. Computational, Mössbauer, XAS, and NRVS studies indicate that protonation of the FeIV-oxo complex most likely occurs on the tripodal ligand, which undergoes a structural change that results in the formation of a new intramolecular H-bond with the oxido ligand that aids in stabilizing the protonated adduct. We suggest that similar protonated high-valent Fe-oxo species may occur in the active sites of proteins. This finding further argues for caution when assigning unverified high-valent Fe-OH species to mechanisms

We thank the U.S. National Institutes of Health (GM050781 to A.S.B., GM49970 to M.P.H., and GM101390 to M.T.G.), the Ministerio de Economia y Competitividad (CTQ2014-59212-P, CTQ2015-70851-ERC), GenCat (2014SGR1202, 2015FIB00165), and the European Fund for Regional Development (UNGI10-4E-801) for financial support, and E. E. Alp, J. Zhao, and M. Hu from the APS in the Argonne National Laboratory for support in collecting NRVS spectra

© Journal of the American Chemical Society, 2016, vol. 138, núm. 40, p. 13143-13146

American Chemical Society (ACS)

Author: Hill, Ethan A.
Weitz, Andrew C.
Onderko, Elizabeth
Romero Rivera, Adrián
Guo, Yisong
Swart, Marcel
Bominaar, , Emile L.
Green, Michael T.
Hendrich, Michael P.
Lacy, David C.
Borovik, A. S.
Date: 2016 October 12
Abstract: High-valent Fe-OH species are often invoked as key intermediates but have only been observed in Compound II of cytochrome P450s. To further address the properties of non-heme FeIV-OH complexes, we demonstrate the reversible protonation of a synthetic FeIV-oxo species containing a tris-urea tripodal ligand. The same protonated FeIV-oxo species can be prepared via oxidation, suggesting that a putative FeV-oxo species was initially generated. Computational, Mössbauer, XAS, and NRVS studies indicate that protonation of the FeIV-oxo complex most likely occurs on the tripodal ligand, which undergoes a structural change that results in the formation of a new intramolecular H-bond with the oxido ligand that aids in stabilizing the protonated adduct. We suggest that similar protonated high-valent Fe-oxo species may occur in the active sites of proteins. This finding further argues for caution when assigning unverified high-valent Fe-OH species to mechanisms
We thank the U.S. National Institutes of Health (GM050781 to A.S.B., GM49970 to M.P.H., and GM101390 to M.T.G.), the Ministerio de Economia y Competitividad (CTQ2014-59212-P, CTQ2015-70851-ERC), GenCat (2014SGR1202, 2015FIB00165), and the European Fund for Regional Development (UNGI10-4E-801) for financial support, and E. E. Alp, J. Zhao, and M. Hu from the APS in the Argonne National Laboratory for support in collecting NRVS spectra
Format: application/pdf
ISSN: 0002-7863 (versió paper)
1520-5126 (versió electrònica)
Document access: http://hdl.handle.net/10256/13149
Language: eng
Publisher: American Chemical Society (ACS)
Collection: MINECO/PE 2015-2017/CTQ2014-59212-P
MINECO/PE 2015-2016/CTQ2015-70851-ERC
AGAUR/2014-2017/2014SGR1202
Reproducció digital del document publicat a: http://dx.doi.org/10.1021/jacs.6b07633
Articles publicats (D-Q)
Is part of: © Journal of the American Chemical Society, 2016, vol. 138, núm. 40, p. 13143-13146
Rights: Tots els drets reservats
Subject: Reaccions químiques
Chemical reactions
Title: Reactivity of an FeIV-Oxo Complex with Protons and Oxidants
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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