Characterized cis-FeV(O)(OH) Intermediate Mimics Enzymatic Oxidations in the Gas Phase

FeV(O)(OH) species have long been proposed to play a key role in a wide range of biomimetic and enzymatic oxidations, including as intermediates in arene dihydroxylation catalyzed by Rieske oxygenases. However, the inability to accumulate these intermediates in solution has thus far prevented their...

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Detalles Bibliográficos
Autores: Borrell Recasens, Margarida, Andris, Erik, Navrátil, Rafael, Roithová, Jana, Costas Salgueiro, Miquel
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2019
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:10256/16379
Acceso en línea:http://hdl.handle.net/10256/16379
Access Level:acceso abierto
Palabra clave:Química bioinorgànica
Fisicoquímica
Catalitzadors
Bioinorganic chemistry
Chemistry, Physical and theoretical
Catalysts
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spelling Characterized cis-FeV(O)(OH) Intermediate Mimics Enzymatic Oxidations in the Gas PhaseBorrell Recasens, MargaridaAndris, ErikNavrátil, RafaelRoithová, JanaCostas Salgueiro, MiquelQuímica bioinorgànicaFisicoquímicaCatalitzadorsBioinorganic chemistryChemistry, Physical and theoreticalCatalystsFeV(O)(OH) species have long been proposed to play a key role in a wide range of biomimetic and enzymatic oxidations, including as intermediates in arene dihydroxylation catalyzed by Rieske oxygenases. However, the inability to accumulate these intermediates in solution has thus far prevented their spectroscopic and chemical characterization. Thus, we use gas-phase ion spectroscopy and reactivity analysis to characterize the highly reactive [FeV(O)(OH)(5tips3tpa)]2+ (32+) complex. The results show that 32+ hydroxylates C-H bonds via a rebound mechanism involving two different ligands at the Fe center and dihydroxylates olefins and arenes. Hence, this study provides a direct evidence of FeV(O)(OH) species in non-heme iron catalysis. Furthermore, the reactivity of 32+ accounts for the unique behavior of Rieske oxygenases. The use of gas-phase ion characterization allows us to address issues related to highly reactive intermediates that other methods are unable to solve in the context of catalysis and enzymologyNature Publishing Group2019info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionpeer-reviewed9 p.application/pdfhttp://hdl.handle.net/10256/16379http://hdl.handle.net/10256/16379Nature Communications, 2019, vol. 10, núm. art. 901Articles publicats (D-Q)Borrell Recasens, Margarida Andris, Erik Navrátil, Rafael Roithová, Jana Costas Salgueiro, Miquel 2019 Characterized cis-FeV(O)(OH) Intermediate Mimics Enzymatic Oxidations in the Gas Phase Nature Communications 10 Art. 901 1 9reponame: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/10.1038/s41467-019-08668-2info:eu-repo/semantics/altIdentifier/issn/2041-1723Reconeixement 4.0 Internacionalhttp://creativecommons.org/licenses/by/4.0info:eu-repo/semantics/openAccessoai:recercat.cat:10256/163792026-05-29T05:05:01Z
dc.title.none.fl_str_mv Characterized cis-FeV(O)(OH) Intermediate Mimics Enzymatic Oxidations in the Gas Phase
title Characterized cis-FeV(O)(OH) Intermediate Mimics Enzymatic Oxidations in the Gas Phase
spellingShingle Characterized cis-FeV(O)(OH) Intermediate Mimics Enzymatic Oxidations in the Gas Phase
Borrell Recasens, Margarida
Química bioinorgànica
Fisicoquímica
Catalitzadors
Bioinorganic chemistry
Chemistry, Physical and theoretical
Catalysts
title_short Characterized cis-FeV(O)(OH) Intermediate Mimics Enzymatic Oxidations in the Gas Phase
title_full Characterized cis-FeV(O)(OH) Intermediate Mimics Enzymatic Oxidations in the Gas Phase
title_fullStr Characterized cis-FeV(O)(OH) Intermediate Mimics Enzymatic Oxidations in the Gas Phase
title_full_unstemmed Characterized cis-FeV(O)(OH) Intermediate Mimics Enzymatic Oxidations in the Gas Phase
title_sort Characterized cis-FeV(O)(OH) Intermediate Mimics Enzymatic Oxidations in the Gas Phase
dc.creator.none.fl_str_mv Borrell Recasens, Margarida
Andris, Erik
Navrátil, Rafael
Roithová, Jana
Costas Salgueiro, Miquel
author Borrell Recasens, Margarida
author_facet Borrell Recasens, Margarida
Andris, Erik
Navrátil, Rafael
Roithová, Jana
Costas Salgueiro, Miquel
author_role author
author2 Andris, Erik
Navrátil, Rafael
Roithová, Jana
Costas Salgueiro, Miquel
author2_role author
author
author
author
dc.subject.none.fl_str_mv Química bioinorgànica
Fisicoquímica
Catalitzadors
Bioinorganic chemistry
Chemistry, Physical and theoretical
Catalysts
topic Química bioinorgànica
Fisicoquímica
Catalitzadors
Bioinorganic chemistry
Chemistry, Physical and theoretical
Catalysts
description FeV(O)(OH) species have long been proposed to play a key role in a wide range of biomimetic and enzymatic oxidations, including as intermediates in arene dihydroxylation catalyzed by Rieske oxygenases. However, the inability to accumulate these intermediates in solution has thus far prevented their spectroscopic and chemical characterization. Thus, we use gas-phase ion spectroscopy and reactivity analysis to characterize the highly reactive [FeV(O)(OH)(5tips3tpa)]2+ (32+) complex. The results show that 32+ hydroxylates C-H bonds via a rebound mechanism involving two different ligands at the Fe center and dihydroxylates olefins and arenes. Hence, this study provides a direct evidence of FeV(O)(OH) species in non-heme iron catalysis. Furthermore, the reactivity of 32+ accounts for the unique behavior of Rieske oxygenases. The use of gas-phase ion characterization allows us to address issues related to highly reactive intermediates that other methods are unable to solve in the context of catalysis and enzymology
publishDate 2019
dc.date.none.fl_str_mv 2019
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
peer-reviewed
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10256/16379
http://hdl.handle.net/10256/16379
url http://hdl.handle.net/10256/16379
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1038/s41467-019-08668-2
info:eu-repo/semantics/altIdentifier/issn/2041-1723
dc.rights.none.fl_str_mv Reconeixement 4.0 Internacional
http://creativecommons.org/licenses/by/4.0
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Reconeixement 4.0 Internacional
http://creativecommons.org/licenses/by/4.0
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 9 p.
application/pdf
dc.publisher.none.fl_str_mv Nature Publishing Group
publisher.none.fl_str_mv Nature Publishing Group
dc.source.none.fl_str_mv Nature Communications, 2019, vol. 10, núm. art. 901
Articles publicats (D-Q)
Borrell Recasens, Margarida Andris, Erik Navrátil, Rafael Roithová, Jana Costas Salgueiro, Miquel 2019 Characterized cis-FeV(O)(OH) Intermediate Mimics Enzymatic Oxidations in the Gas Phase Nature Communications 10 Art. 901 1 9
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
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score 15,811543

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