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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/43398
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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 Técnicas2025-09-29T09:51:50Zoai: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:34982025-09-29 09:51:51.084CONICET 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 |
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13.070432 |