Reactivity of an FeIV-Oxo Complex with Protons and Oxidants
dc.contributor.author
dc.date.accessioned
2016-11-16T12:15:01Z
dc.date.available
2016-11-16T12:15:01Z
dc.date.issued
2016-09-20
dc.identifier.issn
0002-7863
dc.identifier.uri
dc.description.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
dc.description.sponsorship
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
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society (ACS)
dc.relation
info:eu-repo/grantAgreement/MINECO//CTQ2014-59212-P/ES/SPIN STATE AND ENZYMATIC CATALYSIS BASED ON BOTTOM-UP COMPUTATIONAL DESIGN/
info:eu-repo/grantAgreement/MINECO//CTQ2015-70851-ERC/ES/SPIN STATE CATALYSIS THROUGH DENSITY-CONSISTENT MOLECULAR MODELLING/
AGAUR/2014-2017/2014SGR1202
dc.relation.isformatof
Versió postprint del document publicat a: http://dx.doi.org/10.1021/jacs.6b07633
dc.relation.ispartof
© Journal of the American Chemical Society, 2016, vol. 138, núm. 40, p. 13143-13146
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Articles publicats (D-Q)
dc.rights
Tots els drets reservats
dc.subject
dc.title
Reactivity of an FeIV-Oxo Complex with Protons and Oxidants
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.embargo.terms
Cap
dc.date.embargoEndDate
info:eu-repo/date/embargoEnd/2017-09-20
dc.type.version
info:eu-repo/semantics/acceptedVersion
dc.identifier.doi
dc.identifier.idgrec
026295
dc.contributor.funder
dc.type.peerreviewed
peer-reviewed
dc.relation.ProjectAcronym
dc.identifier.eissn
1520-5126