Understanding Heteroatom Effect on Ullmann Copper-Catalyzed Cross-Coupling of X-Arylation (X = NH, O, S) Mechanism

Autores
Andrada, Diego Marcelo; Soria Castro, Silvia Mercedes; Caminos, Daniel Alberto; Argüello, Juan Elias; Peñeñory, Alicia Beatriz
Año de publicación
2017
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Density Functional Theory (DFT) calculations have been carried out in order to unravel the governing reaction mechanism in copper-catalyzed cross-coupling Ullmann type reactions between iodobenzene (1, PhI) and aniline (2-NH, PhNH2), phenol (2-O, PhOH) and thiophenol (2-S, PhSH) with phenanthroline (phen) as the ancillary ligand. Four different pathways for the mechanism were considered namely Oxidative Addition?Reductive Elimination (OA-RE), σ-bond Metathesis (MET), Single Electron Transfer (SET), and Halogen Atom Transfer (HAT). Our results suggest that the OA-RE route, involving CuIII intermediates, is the energetically most favorable pathway for all the systems considered. Interestingly, the rate-determining step is the oxidative addition of the phenyl iodide to the metal center regardless of the nature of the heteroatom. The computed energy barriers in OA increase in the order O < S < NH. Using the Activation Strain Model (ASM) of chemical reactivity, it was found that the strain energy associated with the bending of the copper(I) complex controls the observed reactivity.
Fil: Andrada, Diego Marcelo. Universitat Saarland; Alemania. University of Marburg; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Soria Castro, Silvia Mercedes. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Caminos, Daniel Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Argüello, Juan Elias. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Peñeñory, Alicia Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Materia
COPPER-CATALYST
DENSITY FUNCTIONAL THEORY (DFT)
ACTIVATION STRAIN MODEL
ULLMANN
CROSS-COUPLING
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/43398
Acceder
id CONICETDig_578f5c664152575cbf7330db246a164f
oai_identifier_str oai:ri.conicet.gov.ar:11336/43398
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Understanding Heteroatom Effect on Ullmann Copper-Catalyzed Cross-Coupling of X-Arylation (X = NH, O, S) MechanismAndrada, Diego MarceloSoria Castro, Silvia MercedesCaminos, Daniel AlbertoArgüello, Juan EliasPeñeñory, Alicia BeatrizCOPPER-CATALYSTDENSITY FUNCTIONAL THEORY (DFT)ACTIVATION STRAIN MODELULLMANNCROSS-COUPLINGhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Density Functional Theory (DFT) calculations have been carried out in order to unravel the governing reaction mechanism in copper-catalyzed cross-coupling Ullmann type reactions between iodobenzene (1, PhI) and aniline (2-NH, PhNH2), phenol (2-O, PhOH) and thiophenol (2-S, PhSH) with phenanthroline (phen) as the ancillary ligand. Four different pathways for the mechanism were considered namely Oxidative Addition?Reductive Elimination (OA-RE), σ-bond Metathesis (MET), Single Electron Transfer (SET), and Halogen Atom Transfer (HAT). Our results suggest that the OA-RE route, involving CuIII intermediates, is the energetically most favorable pathway for all the systems considered. Interestingly, the rate-determining step is the oxidative addition of the phenyl iodide to the metal center regardless of the nature of the heteroatom. The computed energy barriers in OA increase in the order O < S < NH. Using the Activation Strain Model (ASM) of chemical reactivity, it was found that the strain energy associated with the bending of the copper(I) complex controls the observed reactivity.Fil: Andrada, Diego Marcelo. Universitat Saarland; Alemania. University of Marburg; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Soria Castro, Silvia Mercedes. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Caminos, Daniel Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Argüello, Juan Elias. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Peñeñory, Alicia Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaMDPI2017-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/43398Andrada, Diego Marcelo; Soria Castro, Silvia Mercedes; Caminos, Daniel Alberto; Argüello, Juan Elias; Peñeñory, Alicia Beatriz; Understanding Heteroatom Effect on Ullmann Copper-Catalyzed Cross-Coupling of X-Arylation (X = NH, O, S) Mechanism; MDPI; Catalysts; 7; 12-2017; 388-4052073-4344CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.3390/catal7120388info:eu-repo/semantics/altIdentifier/url/http://www.mdpi.com/2073-4344/7/12/388info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:21:14Zoai:ri.conicet.gov.ar:11336/43398instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-10-22 11:21:14.912CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Understanding Heteroatom Effect on Ullmann Copper-Catalyzed Cross-Coupling of X-Arylation (X = NH, O, S) Mechanism
title Understanding Heteroatom Effect on Ullmann Copper-Catalyzed Cross-Coupling of X-Arylation (X = NH, O, S) Mechanism
spellingShingle Understanding Heteroatom Effect on Ullmann Copper-Catalyzed Cross-Coupling of X-Arylation (X = NH, O, S) Mechanism
Andrada, Diego Marcelo
COPPER-CATALYST
DENSITY FUNCTIONAL THEORY (DFT)
ACTIVATION STRAIN MODEL
ULLMANN
CROSS-COUPLING
title_short Understanding Heteroatom Effect on Ullmann Copper-Catalyzed Cross-Coupling of X-Arylation (X = NH, O, S) Mechanism
title_full Understanding Heteroatom Effect on Ullmann Copper-Catalyzed Cross-Coupling of X-Arylation (X = NH, O, S) Mechanism
title_fullStr Understanding Heteroatom Effect on Ullmann Copper-Catalyzed Cross-Coupling of X-Arylation (X = NH, O, S) Mechanism
title_full_unstemmed Understanding Heteroatom Effect on Ullmann Copper-Catalyzed Cross-Coupling of X-Arylation (X = NH, O, S) Mechanism
title_sort Understanding Heteroatom Effect on Ullmann Copper-Catalyzed Cross-Coupling of X-Arylation (X = NH, O, S) Mechanism
dc.creator.none.fl_str_mv Andrada, Diego Marcelo
Soria Castro, Silvia Mercedes
Caminos, Daniel Alberto
Argüello, Juan Elias
Peñeñory, Alicia Beatriz
author Andrada, Diego Marcelo
author_facet Andrada, Diego Marcelo
Soria Castro, Silvia Mercedes
Caminos, Daniel Alberto
Argüello, Juan Elias
Peñeñory, Alicia Beatriz
author_role author
author2 Soria Castro, Silvia Mercedes
Caminos, Daniel Alberto
Argüello, Juan Elias
Peñeñory, Alicia Beatriz
author2_role author
author
author
author
dc.subject.none.fl_str_mv COPPER-CATALYST
DENSITY FUNCTIONAL THEORY (DFT)
ACTIVATION STRAIN MODEL
ULLMANN
CROSS-COUPLING
topic COPPER-CATALYST
DENSITY FUNCTIONAL THEORY (DFT)
ACTIVATION STRAIN MODEL
ULLMANN
CROSS-COUPLING
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Density Functional Theory (DFT) calculations have been carried out in order to unravel the governing reaction mechanism in copper-catalyzed cross-coupling Ullmann type reactions between iodobenzene (1, PhI) and aniline (2-NH, PhNH2), phenol (2-O, PhOH) and thiophenol (2-S, PhSH) with phenanthroline (phen) as the ancillary ligand. Four different pathways for the mechanism were considered namely Oxidative Addition?Reductive Elimination (OA-RE), σ-bond Metathesis (MET), Single Electron Transfer (SET), and Halogen Atom Transfer (HAT). Our results suggest that the OA-RE route, involving CuIII intermediates, is the energetically most favorable pathway for all the systems considered. Interestingly, the rate-determining step is the oxidative addition of the phenyl iodide to the metal center regardless of the nature of the heteroatom. The computed energy barriers in OA increase in the order O < S < NH. Using the Activation Strain Model (ASM) of chemical reactivity, it was found that the strain energy associated with the bending of the copper(I) complex controls the observed reactivity.
Fil: Andrada, Diego Marcelo. Universitat Saarland; Alemania. University of Marburg; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Soria Castro, Silvia Mercedes. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Caminos, Daniel Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Argüello, Juan Elias. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Peñeñory, Alicia Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
description Density Functional Theory (DFT) calculations have been carried out in order to unravel the governing reaction mechanism in copper-catalyzed cross-coupling Ullmann type reactions between iodobenzene (1, PhI) and aniline (2-NH, PhNH2), phenol (2-O, PhOH) and thiophenol (2-S, PhSH) with phenanthroline (phen) as the ancillary ligand. Four different pathways for the mechanism were considered namely Oxidative Addition?Reductive Elimination (OA-RE), σ-bond Metathesis (MET), Single Electron Transfer (SET), and Halogen Atom Transfer (HAT). Our results suggest that the OA-RE route, involving CuIII intermediates, is the energetically most favorable pathway for all the systems considered. Interestingly, the rate-determining step is the oxidative addition of the phenyl iodide to the metal center regardless of the nature of the heteroatom. The computed energy barriers in OA increase in the order O < S < NH. Using the Activation Strain Model (ASM) of chemical reactivity, it was found that the strain energy associated with the bending of the copper(I) complex controls the observed reactivity.
publishDate 2017
dc.date.none.fl_str_mv 2017-12
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/43398
Andrada, Diego Marcelo; Soria Castro, Silvia Mercedes; Caminos, Daniel Alberto; Argüello, Juan Elias; Peñeñory, Alicia Beatriz; Understanding Heteroatom Effect on Ullmann Copper-Catalyzed Cross-Coupling of X-Arylation (X = NH, O, S) Mechanism; MDPI; Catalysts; 7; 12-2017; 388-405
2073-4344
CONICET Digital
CONICET
url http://hdl.handle.net/11336/43398
identifier_str_mv Andrada, Diego Marcelo; Soria Castro, Silvia Mercedes; Caminos, Daniel Alberto; Argüello, Juan Elias; Peñeñory, Alicia Beatriz; Understanding Heteroatom Effect on Ullmann Copper-Catalyzed Cross-Coupling of X-Arylation (X = NH, O, S) Mechanism; MDPI; Catalysts; 7; 12-2017; 388-405
2073-4344
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.3390/catal7120388
info:eu-repo/semantics/altIdentifier/url/http://www.mdpi.com/2073-4344/7/12/388
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv MDPI
publisher.none.fl_str_mv MDPI
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
_version_ 1846781713085104128
score 12.982451

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