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...

Descripción completa

Detalles Bibliográficos
Autores: Hill, Ethan A., Weitz, Andrew C., Onderko, Elizabeth, Romero Rivera, Adrian, Guo, Yisong, Swart, Marcel, Bominaar, Emile L., Green, Michael T., Hendrich, Michael P., Lacy, David C., Borovik, A. S.
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2016
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:10256/13149
Acceso en línea:http://hdl.handle.net/10256/13149
Access Level:acceso abierto
Palabra clave:Reaccions químiques
Chemical reactions
id ES_ec3702a7a3ea99743cd8b3e6a88c3e92
oai_identifier_str oai:recercat.cat:10256/13149
network_acronym_str ES
network_name_str España
repository_id_str
spelling Reactivity of an FeIV-Oxo Complex with Protons and OxidantsHill, Ethan A.Weitz, Andrew C.Onderko, ElizabethRomero Rivera, AdrianGuo, YisongSwart, MarcelBominaar, Emile L.Green, Michael T.Hendrich, Michael P.Lacy, David C.Borovik, A. S.Reaccions químiquesChemical reactionsHigh-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 mechanismsWe 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 spectraAmerican Chemical Society (ACS)Ministerio de Economía y Competitividad (Espanya)Generalitat de Catalunya. Agència de Gestió d'Ajuts Universitaris i de Recercainfo2016info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionpeer-reviewedapplication/pdfhttp://hdl.handle.net/10256/13149© Journal of the American Chemical Society, 2016, vol. 138, núm. 40, p. 13143-13146Articles publicats (D-Q)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)Inglésinfo:eu-repo/semantics/altIdentifier/doi/10.1021/jacs.6b07633info:eu-repo/semantics/altIdentifier/issn/0002-7863info:eu-repo/semantics/altIdentifier/eissn/1520-5126info:eu-repo/grantAgreement/MINECO//CTQ2014-59212-Pinfo:eu-repo/grantAgreement/MINECO//CTQ2015-70851-ERCAGAUR/2014-2017/2014SGR1202Tots els drets reservatsinfo:eu-repo/semantics/openAccessoai:recercat.cat:10256/131492026-05-29T05:05:01Z
dc.title.none.fl_str_mv Reactivity of an FeIV-Oxo Complex with Protons and Oxidants
title Reactivity of an FeIV-Oxo Complex with Protons and Oxidants
spellingShingle Reactivity of an FeIV-Oxo Complex with Protons and Oxidants
Hill, Ethan A.
Reaccions químiques
Chemical reactions
title_short Reactivity of an FeIV-Oxo Complex with Protons and Oxidants
title_full Reactivity of an FeIV-Oxo Complex with Protons and Oxidants
title_fullStr Reactivity of an FeIV-Oxo Complex with Protons and Oxidants
title_full_unstemmed Reactivity of an FeIV-Oxo Complex with Protons and Oxidants
title_sort Reactivity of an FeIV-Oxo Complex with Protons and Oxidants
dc.creator.none.fl_str_mv Hill, Ethan A.
Weitz, Andrew C.
Onderko, Elizabeth
Romero Rivera, Adrian
Guo, Yisong
Swart, Marcel
Bominaar, Emile L.
Green, Michael T.
Hendrich, Michael P.
Lacy, David C.
Borovik, A. S.
author Hill, Ethan A.
author_facet Hill, Ethan A.
Weitz, Andrew C.
Onderko, Elizabeth
Romero Rivera, Adrian
Guo, Yisong
Swart, Marcel
Bominaar, Emile L.
Green, Michael T.
Hendrich, Michael P.
Lacy, David C.
Borovik, A. S.
author_role author
author2 Weitz, Andrew C.
Onderko, Elizabeth
Romero Rivera, Adrian
Guo, Yisong
Swart, Marcel
Bominaar, Emile L.
Green, Michael T.
Hendrich, Michael P.
Lacy, David C.
Borovik, A. S.
author2_role author
author
author
author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Economía y Competitividad (Espanya)
Generalitat de Catalunya. Agència de Gestió d'Ajuts Universitaris i de Recerca
dc.subject.none.fl_str_mv Reaccions químiques
Chemical reactions
topic Reaccions químiques
Chemical reactions
description 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
publishDate 2016
dc.date.none.fl_str_mv 2016
info
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
peer-reviewed
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10256/13149
url http://hdl.handle.net/10256/13149
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/jacs.6b07633
info:eu-repo/semantics/altIdentifier/issn/0002-7863
info:eu-repo/semantics/altIdentifier/eissn/1520-5126
info:eu-repo/grantAgreement/MINECO//CTQ2014-59212-P
info:eu-repo/grantAgreement/MINECO//CTQ2015-70851-ERC
AGAUR/2014-2017/2014SGR1202
dc.rights.none.fl_str_mv Tots els drets reservats
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Tots els drets reservats
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Chemical Society (ACS)
publisher.none.fl_str_mv American Chemical Society (ACS)
dc.source.none.fl_str_mv © Journal of the American Chemical Society, 2016, vol. 138, núm. 40, p. 13143-13146
Articles publicats (D-Q)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
_version_ 1869423295748636673
score 15.812429

Similares en LA Referencia