A competing, dual mechanism for catalytic direct benzene hydroxylation from combined experimental-DFT studies

A dual mechanism for direct benzene catalytic hydroxylation is described. Experimental studies and DFT calculations have provided a mechanistic explanation for the acid-free, TpxCu-catalyzed hydroxylation of benzene with hydrogen peroxide (Tpx = hydrotrispyrazolylborate ligand). In contrast with oth...

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Detalles Bibliográficos
Autores: Vilella, Laia, Conde Alcántara, Ana Isabel, Ballcells, David, Díaz Requejo, María Mar, Lledós, Agustín, Pérez Romero, Pedro José
Tipo de recurso: artículo
Fecha de publicación:2017
País:España
Institución:Universidad de Huelva (UHU)
Repositorio:Arias Montano. Repositorio Institucional de la Universidad de Huelva
Idioma:inglés
OAI Identifier:oai:ariasmontano.uhu.es:10272/15234
Acceso en línea:http://hdl.handle.net/10272/15234
Access Level:acceso abierto
Palabra clave:Hydroxylation
Hidrogen-peroxide
Molecular-oxygen
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spelling A competing, dual mechanism for catalytic direct benzene hydroxylation from combined experimental-DFT studiesVilella, LaiaConde Alcántara, Ana IsabelBallcells, DavidDíaz Requejo, María MarLledós, AgustínPérez Romero, Pedro JoséHydroxylationHidrogen-peroxideHydroxylationMolecular-oxygenA dual mechanism for direct benzene catalytic hydroxylation is described. Experimental studies and DFT calculations have provided a mechanistic explanation for the acid-free, TpxCu-catalyzed hydroxylation of benzene with hydrogen peroxide (Tpx = hydrotrispyrazolylborate ligand). In contrast with other catalytic systems that promote this transformation through Fenton-like pathways, this system operates through a copper-oxyl intermediate that may interact with the arene ring following two different, competitive routes: (a) electrophilic aromatic substitution, with the copper-oxyl species acting as the formal electrophile, and (b) the so-called rebound mechanism, in which the hydrogen is abstracted by the Cu–O moiety prior to the C–O bond formation. Both pathways contribute to the global transformation albeit to different extents, the electrophilic substitution route seeming to be largely favoured.Royal Society of Chemistry20172017-01-0120172017-01-01journal articlehttp://purl.org/coar/resource_type/c_6501info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10272/15234reponame:Arias Montano. Repositorio Institucional de la Universidad de Huelvainstname:Universidad de Huelva (UHU)InglésengMinisterio de Economía y Competitividad http://dx.doi.org/10.13039/501100003329 Not available Not availableopen accesshttp://purl.org/coar/access_right/c_abf2Atribución-NoComercial-SinDerivadas 3.0 Españahttp://creativecommons.org/licenses/by-nc-nd/3.0/es/info:eu-repo/semantics/openAccessoai:ariasmontano.uhu.es:10272/152342026-06-02T14:58:11Z
dc.title.none.fl_str_mv A competing, dual mechanism for catalytic direct benzene hydroxylation from combined experimental-DFT studies
title A competing, dual mechanism for catalytic direct benzene hydroxylation from combined experimental-DFT studies
spellingShingle A competing, dual mechanism for catalytic direct benzene hydroxylation from combined experimental-DFT studies
Vilella, Laia
Hydroxylation
Hidrogen-peroxide
Hydroxylation
Molecular-oxygen
title_short A competing, dual mechanism for catalytic direct benzene hydroxylation from combined experimental-DFT studies
title_full A competing, dual mechanism for catalytic direct benzene hydroxylation from combined experimental-DFT studies
title_fullStr A competing, dual mechanism for catalytic direct benzene hydroxylation from combined experimental-DFT studies
title_full_unstemmed A competing, dual mechanism for catalytic direct benzene hydroxylation from combined experimental-DFT studies
title_sort A competing, dual mechanism for catalytic direct benzene hydroxylation from combined experimental-DFT studies
dc.creator.none.fl_str_mv Vilella, Laia
Conde Alcántara, Ana Isabel
Ballcells, David
Díaz Requejo, María Mar
Lledós, Agustín
Pérez Romero, Pedro José
author Vilella, Laia
author_facet Vilella, Laia
Conde Alcántara, Ana Isabel
Ballcells, David
Díaz Requejo, María Mar
Lledós, Agustín
Pérez Romero, Pedro José
author_role author
author2 Conde Alcántara, Ana Isabel
Ballcells, David
Díaz Requejo, María Mar
Lledós, Agustín
Pérez Romero, Pedro José
author2_role author
author
author
author
author
dc.contributor.none.fl_str_mv
dc.subject.none.fl_str_mv Hydroxylation
Hidrogen-peroxide
Hydroxylation
Molecular-oxygen
topic Hydroxylation
Hidrogen-peroxide
Hydroxylation
Molecular-oxygen
description A dual mechanism for direct benzene catalytic hydroxylation is described. Experimental studies and DFT calculations have provided a mechanistic explanation for the acid-free, TpxCu-catalyzed hydroxylation of benzene with hydrogen peroxide (Tpx = hydrotrispyrazolylborate ligand). In contrast with other catalytic systems that promote this transformation through Fenton-like pathways, this system operates through a copper-oxyl intermediate that may interact with the arene ring following two different, competitive routes: (a) electrophilic aromatic substitution, with the copper-oxyl species acting as the formal electrophile, and (b) the so-called rebound mechanism, in which the hydrogen is abstracted by the Cu–O moiety prior to the C–O bond formation. Both pathways contribute to the global transformation albeit to different extents, the electrophilic substitution route seeming to be largely favoured.
publishDate 2017
dc.date.none.fl_str_mv 2017
2017-01-01
2017
2017-01-01
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10272/15234
url http://hdl.handle.net/10272/15234
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.relation.none.fl_str_mv Ministerio de Economía y Competitividad http://dx.doi.org/10.13039/501100003329 Not available Not available
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Atribución-NoComercial-SinDerivadas 3.0 España
http://creativecommons.org/licenses/by-nc-nd/3.0/es/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
Atribución-NoComercial-SinDerivadas 3.0 España
http://creativecommons.org/licenses/by-nc-nd/3.0/es/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
dc.source.none.fl_str_mv reponame:Arias Montano. Repositorio Institucional de la Universidad de Huelva
instname:Universidad de Huelva (UHU)
instname_str Universidad de Huelva (UHU)
reponame_str Arias Montano. Repositorio Institucional de la Universidad de Huelva
collection Arias Montano. Repositorio Institucional de la Universidad de Huelva
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15.811543

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