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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

American Chemical Society (ACS)

Manager: Ministerio de Economía y Competitividad (Espanya)
Generalitat de Catalunya. Agència de Gestió d’Ajuts Universitaris i de Recerca
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.
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
Document access: http://hdl.handle.net/2072/298538
Language: eng
Publisher: American Chemical Society (ACS)
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: Recercat

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