DFT Study of Thermal 1,3-Dipolar Cycloaddition Reactions between Alkynyl Metal(0) Fischer Carbene Complexes and 3 H -1,2-Dithiole-3-thione Derivatives

Autores
Andrada, Diego Marcelo; Granados, Alejandro Manuel; Solà, Miquel; Fernández, Israel
Año de publicación
2011
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The thermal 1,3-dipolar cycloaddition reaction between alkynyl metal(0) Fischer carbenes and 5-methyl-3H-1,2-dithiole-3-thione to yield 1,3-dithiafulvene has been studied computationally within the Density Functional Theory framework. The transformations involving Fischer carbene complexes and their isolobal analogues (organic esters and corresponding Lewis acid complexes) were compared in terms of regioselectivity, barrier and reaction energies, synchronicity, and aromaticity of the corresponding transition states. These reactions are found to be concerted and completely regioselective toward the formation of the Z-1,3-dithiafulvene isomer, which is kinetically favored. DFT calculations are in good agreement with the experimental outcome of the process, which can be explained by means of the corresponding frontier molecular orbitals of reactants and their electrostatic potentials.
Fil: Andrada, Diego Marcelo. 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: Granados, Alejandro Manuel. 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: Solà, Miquel. Universidad de Girona; España
Fil: Fernández, Israel. Universidad Complutense de Madrid; España
Materia
DFT
Cycloaddition
Alkynyl Metal(0) Fischer Carbene Complexes
3H-1,2-Dithiole-3- thione
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:11336/268264
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/268264
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling DFT Study of Thermal 1,3-Dipolar Cycloaddition Reactions between Alkynyl Metal(0) Fischer Carbene Complexes and 3 H -1,2-Dithiole-3-thione DerivativesAndrada, Diego MarceloGranados, Alejandro ManuelSolà, MiquelFernández, IsraelDFTCycloadditionAlkynyl Metal(0) Fischer Carbene Complexes3H-1,2-Dithiole-3- thionehttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The thermal 1,3-dipolar cycloaddition reaction between alkynyl metal(0) Fischer carbenes and 5-methyl-3H-1,2-dithiole-3-thione to yield 1,3-dithiafulvene has been studied computationally within the Density Functional Theory framework. The transformations involving Fischer carbene complexes and their isolobal analogues (organic esters and corresponding Lewis acid complexes) were compared in terms of regioselectivity, barrier and reaction energies, synchronicity, and aromaticity of the corresponding transition states. These reactions are found to be concerted and completely regioselective toward the formation of the Z-1,3-dithiafulvene isomer, which is kinetically favored. DFT calculations are in good agreement with the experimental outcome of the process, which can be explained by means of the corresponding frontier molecular orbitals of reactants and their electrostatic potentials.Fil: Andrada, Diego Marcelo. 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: Granados, Alejandro Manuel. 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: Solà, Miquel. Universidad de Girona; EspañaFil: Fernández, Israel. Universidad Complutense de Madrid; EspañaAmerican Chemical Society2011-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/268264Andrada, Diego Marcelo; Granados, Alejandro Manuel; Solà, Miquel; Fernández, Israel; DFT Study of Thermal 1,3-Dipolar Cycloaddition Reactions between Alkynyl Metal(0) Fischer Carbene Complexes and 3 H -1,2-Dithiole-3-thione Derivatives; American Chemical Society; Organometallics; 30; 3; 1-2011; 466-4760276-7333CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/om1007105info:eu-repo/semantics/altIdentifier/doi/10.1021/om1007105info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-17T11:28:28Zoai:ri.conicet.gov.ar:11336/268264instacron: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:34982025-09-17 11:28:28.288CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv DFT Study of Thermal 1,3-Dipolar Cycloaddition Reactions between Alkynyl Metal(0) Fischer Carbene Complexes and 3 H -1,2-Dithiole-3-thione Derivatives
title DFT Study of Thermal 1,3-Dipolar Cycloaddition Reactions between Alkynyl Metal(0) Fischer Carbene Complexes and 3 H -1,2-Dithiole-3-thione Derivatives
spellingShingle DFT Study of Thermal 1,3-Dipolar Cycloaddition Reactions between Alkynyl Metal(0) Fischer Carbene Complexes and 3 H -1,2-Dithiole-3-thione Derivatives
Andrada, Diego Marcelo
DFT
Cycloaddition
Alkynyl Metal(0) Fischer Carbene Complexes
3H-1,2-Dithiole-3- thione
title_short DFT Study of Thermal 1,3-Dipolar Cycloaddition Reactions between Alkynyl Metal(0) Fischer Carbene Complexes and 3 H -1,2-Dithiole-3-thione Derivatives
title_full DFT Study of Thermal 1,3-Dipolar Cycloaddition Reactions between Alkynyl Metal(0) Fischer Carbene Complexes and 3 H -1,2-Dithiole-3-thione Derivatives
title_fullStr DFT Study of Thermal 1,3-Dipolar Cycloaddition Reactions between Alkynyl Metal(0) Fischer Carbene Complexes and 3 H -1,2-Dithiole-3-thione Derivatives
title_full_unstemmed DFT Study of Thermal 1,3-Dipolar Cycloaddition Reactions between Alkynyl Metal(0) Fischer Carbene Complexes and 3 H -1,2-Dithiole-3-thione Derivatives
title_sort DFT Study of Thermal 1,3-Dipolar Cycloaddition Reactions between Alkynyl Metal(0) Fischer Carbene Complexes and 3 H -1,2-Dithiole-3-thione Derivatives
dc.creator.none.fl_str_mv Andrada, Diego Marcelo
Granados, Alejandro Manuel
Solà, Miquel
Fernández, Israel
author Andrada, Diego Marcelo
author_facet Andrada, Diego Marcelo
Granados, Alejandro Manuel
Solà, Miquel
Fernández, Israel
author_role author
author2 Granados, Alejandro Manuel
Solà, Miquel
Fernández, Israel
author2_role author
author
author
dc.subject.none.fl_str_mv DFT
Cycloaddition
Alkynyl Metal(0) Fischer Carbene Complexes
3H-1,2-Dithiole-3- thione
topic DFT
Cycloaddition
Alkynyl Metal(0) Fischer Carbene Complexes
3H-1,2-Dithiole-3- thione
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The thermal 1,3-dipolar cycloaddition reaction between alkynyl metal(0) Fischer carbenes and 5-methyl-3H-1,2-dithiole-3-thione to yield 1,3-dithiafulvene has been studied computationally within the Density Functional Theory framework. The transformations involving Fischer carbene complexes and their isolobal analogues (organic esters and corresponding Lewis acid complexes) were compared in terms of regioselectivity, barrier and reaction energies, synchronicity, and aromaticity of the corresponding transition states. These reactions are found to be concerted and completely regioselective toward the formation of the Z-1,3-dithiafulvene isomer, which is kinetically favored. DFT calculations are in good agreement with the experimental outcome of the process, which can be explained by means of the corresponding frontier molecular orbitals of reactants and their electrostatic potentials.
Fil: Andrada, Diego Marcelo. 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: Granados, Alejandro Manuel. 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: Solà, Miquel. Universidad de Girona; España
Fil: Fernández, Israel. Universidad Complutense de Madrid; España
description The thermal 1,3-dipolar cycloaddition reaction between alkynyl metal(0) Fischer carbenes and 5-methyl-3H-1,2-dithiole-3-thione to yield 1,3-dithiafulvene has been studied computationally within the Density Functional Theory framework. The transformations involving Fischer carbene complexes and their isolobal analogues (organic esters and corresponding Lewis acid complexes) were compared in terms of regioselectivity, barrier and reaction energies, synchronicity, and aromaticity of the corresponding transition states. These reactions are found to be concerted and completely regioselective toward the formation of the Z-1,3-dithiafulvene isomer, which is kinetically favored. DFT calculations are in good agreement with the experimental outcome of the process, which can be explained by means of the corresponding frontier molecular orbitals of reactants and their electrostatic potentials.
publishDate 2011
dc.date.none.fl_str_mv 2011-01
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/11336/268264
Andrada, Diego Marcelo; Granados, Alejandro Manuel; Solà, Miquel; Fernández, Israel; DFT Study of Thermal 1,3-Dipolar Cycloaddition Reactions between Alkynyl Metal(0) Fischer Carbene Complexes and 3 H -1,2-Dithiole-3-thione Derivatives; American Chemical Society; Organometallics; 30; 3; 1-2011; 466-476
0276-7333
CONICET Digital
CONICET
url http://hdl.handle.net/11336/268264
identifier_str_mv Andrada, Diego Marcelo; Granados, Alejandro Manuel; Solà, Miquel; Fernández, Israel; DFT Study of Thermal 1,3-Dipolar Cycloaddition Reactions between Alkynyl Metal(0) Fischer Carbene Complexes and 3 H -1,2-Dithiole-3-thione Derivatives; American Chemical Society; Organometallics; 30; 3; 1-2011; 466-476
0276-7333
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/om1007105
info:eu-repo/semantics/altIdentifier/doi/10.1021/om1007105
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
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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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score 13.001348

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