Computational Insight into the Mechanism of Alkane Hydroxylation by Non-heme Fe(PyTACN) Iron Complexes. Effects of the Substrate and Solvent

The reaction mechanisms for alkane hydroxylation catalyzed by non-heme FeVO complexes presented in the literature vary from rebound stepwise to concerted highly asynchronous processes. The origin of these important differences is still not completely understood. Herein, in order to clarify this appa...

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Autores: Postils Ribó, Verònica, Company Casadevall, Anna, Solà i Puig, Miquel, Costas Salgueiro, Miquel, Luis Luis, Josep Maria
Formato: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2015
País:España
Recursos: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:10256/11165
Acesso em linha:http://hdl.handle.net/10256/11165
Access Level:acceso abierto
Palavra-chave:Alquens
Oxidació
Catàlisi
Ferro -- Compostos
Alkenes
Oxidation
Catalysis
Iron compounds
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network_name_str España
repository_id_str
dc.title.none.fl_str_mv Computational Insight into the Mechanism of Alkane Hydroxylation by Non-heme Fe(PyTACN) Iron Complexes. Effects of the Substrate and Solvent
title Computational Insight into the Mechanism of Alkane Hydroxylation by Non-heme Fe(PyTACN) Iron Complexes. Effects of the Substrate and Solvent
spellingShingle Computational Insight into the Mechanism of Alkane Hydroxylation by Non-heme Fe(PyTACN) Iron Complexes. Effects of the Substrate and Solvent
Postils Ribó, Verònica
Alquens
Oxidació
Catàlisi
Ferro -- Compostos
Alkenes
Oxidation
Catalysis
Iron compounds
title_short Computational Insight into the Mechanism of Alkane Hydroxylation by Non-heme Fe(PyTACN) Iron Complexes. Effects of the Substrate and Solvent
title_full Computational Insight into the Mechanism of Alkane Hydroxylation by Non-heme Fe(PyTACN) Iron Complexes. Effects of the Substrate and Solvent
title_fullStr Computational Insight into the Mechanism of Alkane Hydroxylation by Non-heme Fe(PyTACN) Iron Complexes. Effects of the Substrate and Solvent
title_full_unstemmed Computational Insight into the Mechanism of Alkane Hydroxylation by Non-heme Fe(PyTACN) Iron Complexes. Effects of the Substrate and Solvent
title_sort Computational Insight into the Mechanism of Alkane Hydroxylation by Non-heme Fe(PyTACN) Iron Complexes. Effects of the Substrate and Solvent
dc.creator.none.fl_str_mv Postils Ribó, Verònica
Company Casadevall, Anna
Solà i Puig, Miquel
Costas Salgueiro, Miquel
Luis Luis, Josep Maria
author Postils Ribó, Verònica
author_facet Postils Ribó, Verònica
Company Casadevall, Anna
Solà i Puig, Miquel
Costas Salgueiro, Miquel
Luis Luis, Josep Maria
author_role author
author2 Company Casadevall, Anna
Solà i Puig, Miquel
Costas Salgueiro, Miquel
Luis Luis, Josep Maria
author2_role 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 Alquens
Oxidació
Catàlisi
Ferro -- Compostos
Alkenes
Oxidation
Catalysis
Iron compounds
topic Alquens
Oxidació
Catàlisi
Ferro -- Compostos
Alkenes
Oxidation
Catalysis
Iron compounds
description The reaction mechanisms for alkane hydroxylation catalyzed by non-heme FeVO complexes presented in the literature vary from rebound stepwise to concerted highly asynchronous processes. The origin of these important differences is still not completely understood. Herein, in order to clarify this apparent inconsistency, the hydroxylation of a series of alkanes (methane and substrates bearing primary, secondary, and tertiary C<br>H bonds) through a FeVO species, [FeV(O)(OH)(PyTACN)]2+ (PyTACN = 1-(2′-pyridylmethyl)-4,7-dimethyl-1,4,7-triazacyclononane), has been computationally examined at the gas phase and in acetonitrile solution. The initial breaking of the C<br>H bond can occur via hydrogen atom transfer (HAT), leading to an intermediate where there is an interaction between the radical substrate and [FeIV(OH)2(PyTACN)]2+, or through hydride transfer to form a cationic substrate interacting with the [FeIII(OH)2(PyTACN)]+ species. Our calculations show the following: (i) except for methane in the rest of the alkanes studied, the intermediate formed by R+ and [FeIII(OH)2(PyTACN)]+ is more stable than that involving the alkyl radical and the [FeIV(OH)2(PyTACN)]2+ complex; (ii) in spite of (i), the first step of the reaction mechanism for all substrates is a HAT instead of hydride abstraction; (iii) the HAT is the rate-determining step for all analyzed cases; and (iv) the barrier for the HAT decreases along methane → primary → secondary → tertiary carbon. The second part of the reaction mechanism corresponds to the rebound process. Therefore, the stereospecific hydroxylation of alkane C<br>H bonds by non-heme FeV(O) species occurs through a rebound stepwise mechanism that resembles that taking place at heme analogues. Finally, our study also shows that, to properly describe alkane hydroxylation processes mediated by FeVO species, it is essential to consider the solvent effects during geometry optimizations. The use of gas-phase geometries explains the variety of mechanisms for the hydroxylation of alkanes reported in the literature
publishDate 2015
dc.date.none.fl_str_mv 2015
info
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10256/11165
http://hdl.handle.net/10256/11165
url http://hdl.handle.net/10256/11165
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/acs.inorgchem.5b00583
info:eu-repo/semantics/altIdentifier/issn/0020-1669
info:eu-repo/semantics/altIdentifier/eissn/1520-510X
info:eu-repo/grantAgreement/MINECO//CTQ2014-54306-P
info:eu-repo/grantAgreement/MINECO//CTQ2014-52525-P
info:eu-repo/grantAgreement/MINECO//CTQ2012-37420-C02-01
AGAUR/2014-2016/2014 SGR-931
AGAUR/2014-2016/2014 SGR-862
info:eu-repo/grantAgreement/EC/FP7/239910
info:eu-repo/grantAgreement/EC/FP7/303522
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 14 p.
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 © Inorganic Chemistry, 2015, vol. 54, núm. 17, p. 8223-8236
Articles publicats (D-Q)
Postils, Verònica Company Casadevall, Anna Solà i Puig, Miquel Costas Salgueiro, Miquel Luis Luis, Josep Maria 2015 Computational Insight into the Mechanism of Alkane Hydroxylation by Non-heme Fe(PyTACN) Iron Complexes. Effects of the Substrate and Solvent Inorganic Chemistry 54 17 8223 8236
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_ 1869413103979986944
spelling Computational Insight into the Mechanism of Alkane Hydroxylation by Non-heme Fe(PyTACN) Iron Complexes. Effects of the Substrate and SolventPostils Ribó, VerònicaCompany Casadevall, AnnaSolà i Puig, MiquelCostas Salgueiro, MiquelLuis Luis, Josep MariaAlquensOxidacióCatàlisiFerro -- CompostosAlkenesOxidationCatalysisIron compoundsThe reaction mechanisms for alkane hydroxylation catalyzed by non-heme FeVO complexes presented in the literature vary from rebound stepwise to concerted highly asynchronous processes. The origin of these important differences is still not completely understood. Herein, in order to clarify this apparent inconsistency, the hydroxylation of a series of alkanes (methane and substrates bearing primary, secondary, and tertiary C<br>H bonds) through a FeVO species, [FeV(O)(OH)(PyTACN)]2+ (PyTACN = 1-(2′-pyridylmethyl)-4,7-dimethyl-1,4,7-triazacyclononane), has been computationally examined at the gas phase and in acetonitrile solution. The initial breaking of the C<br>H bond can occur via hydrogen atom transfer (HAT), leading to an intermediate where there is an interaction between the radical substrate and [FeIV(OH)2(PyTACN)]2+, or through hydride transfer to form a cationic substrate interacting with the [FeIII(OH)2(PyTACN)]+ species. Our calculations show the following: (i) except for methane in the rest of the alkanes studied, the intermediate formed by R+ and [FeIII(OH)2(PyTACN)]+ is more stable than that involving the alkyl radical and the [FeIV(OH)2(PyTACN)]2+ complex; (ii) in spite of (i), the first step of the reaction mechanism for all substrates is a HAT instead of hydride abstraction; (iii) the HAT is the rate-determining step for all analyzed cases; and (iv) the barrier for the HAT decreases along methane → primary → secondary → tertiary carbon. The second part of the reaction mechanism corresponds to the rebound process. Therefore, the stereospecific hydroxylation of alkane C<br>H bonds by non-heme FeV(O) species occurs through a rebound stepwise mechanism that resembles that taking place at heme analogues. Finally, our study also shows that, to properly describe alkane hydroxylation processes mediated by FeVO species, it is essential to consider the solvent effects during geometry optimizations. The use of gas-phase geometries explains the variety of mechanisms for the hydroxylation of alkanes reported in the literatureThis work has been supported by Ministerio de Economiá y Competitividad of Spain (Projects CTQ2014-54306-P, CTQ2014-52525-P, and CTQ2012-37420-C02-01, Ramón y Cajal contract to A.C., and grant No. BES-2012-052801 to V.P.), Generalitat de Catalunya (project numbers 2014SGR931, 2014SGR862, Xarxa de Refereǹ cia en Quiḿ ica Teor̀ ica i Computacional, and ICREA Academia prizes for M.S. and M.C.), the European Commission (ERC-2009-StG-239910 to M.C. and FP7-PEOPLE-2011-CIG-303522 to A.C.), and European Fund for Regional Development (FEDER grant UNGI10-4E-801)American Chemical Society (ACS)Ministerio de Economía y Competitividad (Espanya)Generalitat de Catalunya. Agència de Gestió d'Ajuts Universitaris i de Recercainfo2015info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersion14 p.application/pdfhttp://hdl.handle.net/10256/11165http://hdl.handle.net/10256/11165© Inorganic Chemistry, 2015, vol. 54, núm. 17, p. 8223-8236Articles publicats (D-Q)Postils, Verònica Company Casadevall, Anna Solà i Puig, Miquel Costas Salgueiro, Miquel Luis Luis, Josep Maria 2015 Computational Insight into the Mechanism of Alkane Hydroxylation by Non-heme Fe(PyTACN) Iron Complexes. Effects of the Substrate and Solvent Inorganic Chemistry 54 17 8223 8236reponame: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/acs.inorgchem.5b00583info:eu-repo/semantics/altIdentifier/issn/0020-1669info:eu-repo/semantics/altIdentifier/eissn/1520-510Xinfo:eu-repo/grantAgreement/MINECO//CTQ2014-54306-Pinfo:eu-repo/grantAgreement/MINECO//CTQ2014-52525-Pinfo:eu-repo/grantAgreement/MINECO//CTQ2012-37420-C02-01AGAUR/2014-2016/2014 SGR-931AGAUR/2014-2016/2014 SGR-862info:eu-repo/grantAgreement/EC/FP7/239910info:eu-repo/grantAgreement/EC/FP7/303522Tots els drets reservatsinfo:eu-repo/semantics/openAccessoai:recercat.cat:10256/111652026-05-29T05:05:01Z
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