An Anionic Mesoionic Carbene (anMIC) and its Transformation to Metallo MIC‐Boranes: Synthesis and Properties

Autores
Rudolf, Richard; Todorovski, Andrej; Lederer, Vera; Neuman, Nicolás Ignacio; Schubert, Hartmut; Sarkar, Biprajit
Año de publicación
2025
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Neutral mesoionic carbenes (MICs) based on a 1,2,3-triazole core have had a strong impact on various branches of chemistry such as homogeneous catalysis, electrocatalysis, and photochemistry/photophysics. We present here the first general synthesis of anionic mesoionic carbenes (anMICs) based on a 1,2,3-triazole core and a borate backbone. The free anMIC is stable in solution under an inert atmosphere at low temperatures, and can be stored for several weeks. Analysis of donor properties shows that these anMICs are extremely strong σ-donors, bypassing the donor properties of strong donors such as MICs, NHCs, anionic NHCs and N-heterocyclic olefins. The room temperature conversion of the free anMICs leads to three equally interesting compound classes: an amide-coordinated borane based on a MIC-borane backbone, a polymeric triazolide and an amide-coordinated metallo-MIC-borane. The metallo-MIC-borane is an interesting precursor for the synthesis of further amide-coordinated MIC-borane compounds. Quantum chemical calculations have been used to elucidate the mechanism of transformation of the anMICs. Gold(I) complexes of the anMIC ligands are potent catalysts for the hydroamination of alkynes without the need for any additional reagents. We thus introduce three new categories of mesoionic compounds here with potential for different branches of chemistry and beyond.
Fil: Rudolf, Richard. Universitat Stuttgart; Alemania
Fil: Todorovski, Andrej. Universitat Stuttgart; Alemania
Fil: Lederer, Vera. Universitat Stuttgart; Alemania
Fil: Neuman, Nicolás Ignacio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Schubert, Hartmut. Universitat Stuttgart; Alemania
Fil: Sarkar, Biprajit. Universitat Stuttgart; Alemania
Materia
CARBENES
MESOIONIC
SIGMA DONOR
CLICK REACTION
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/279807
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/279807
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network_name_str CONICET Digital (CONICET)
spelling An Anionic Mesoionic Carbene (anMIC) and its Transformation to Metallo MIC‐Boranes: Synthesis and PropertiesRudolf, RichardTodorovski, AndrejLederer, VeraNeuman, Nicolás IgnacioSchubert, HartmutSarkar, BiprajitCARBENESMESOIONICSIGMA DONORCLICK REACTIONhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Neutral mesoionic carbenes (MICs) based on a 1,2,3-triazole core have had a strong impact on various branches of chemistry such as homogeneous catalysis, electrocatalysis, and photochemistry/photophysics. We present here the first general synthesis of anionic mesoionic carbenes (anMICs) based on a 1,2,3-triazole core and a borate backbone. The free anMIC is stable in solution under an inert atmosphere at low temperatures, and can be stored for several weeks. Analysis of donor properties shows that these anMICs are extremely strong σ-donors, bypassing the donor properties of strong donors such as MICs, NHCs, anionic NHCs and N-heterocyclic olefins. The room temperature conversion of the free anMICs leads to three equally interesting compound classes: an amide-coordinated borane based on a MIC-borane backbone, a polymeric triazolide and an amide-coordinated metallo-MIC-borane. The metallo-MIC-borane is an interesting precursor for the synthesis of further amide-coordinated MIC-borane compounds. Quantum chemical calculations have been used to elucidate the mechanism of transformation of the anMICs. Gold(I) complexes of the anMIC ligands are potent catalysts for the hydroamination of alkynes without the need for any additional reagents. We thus introduce three new categories of mesoionic compounds here with potential for different branches of chemistry and beyond.Fil: Rudolf, Richard. Universitat Stuttgart; AlemaniaFil: Todorovski, Andrej. Universitat Stuttgart; AlemaniaFil: Lederer, Vera. Universitat Stuttgart; AlemaniaFil: Neuman, Nicolás Ignacio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; ArgentinaFil: Schubert, Hartmut. Universitat Stuttgart; AlemaniaFil: Sarkar, Biprajit. Universitat Stuttgart; AlemaniaWiley VCH Verlag2025-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/279807Rudolf, Richard; Todorovski, Andrej; Lederer, Vera; Neuman, Nicolás Ignacio; Schubert, Hartmut; et al.; An Anionic Mesoionic Carbene (anMIC) and its Transformation to Metallo MIC‐Boranes: Synthesis and Properties; Wiley VCH Verlag; Angewandte Chemie; 64; 13; 1-2025; 1-151433-7851CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/10.1002/anie.202422702info:eu-repo/semantics/altIdentifier/doi/10.1002/anie.202422702info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2026-02-26T10:24:49Zoai:ri.conicet.gov.ar:11336/279807instacron: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:34982026-02-26 10:24:50.17CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv An Anionic Mesoionic Carbene (anMIC) and its Transformation to Metallo MIC‐Boranes: Synthesis and Properties
title An Anionic Mesoionic Carbene (anMIC) and its Transformation to Metallo MIC‐Boranes: Synthesis and Properties
spellingShingle An Anionic Mesoionic Carbene (anMIC) and its Transformation to Metallo MIC‐Boranes: Synthesis and Properties
Rudolf, Richard
CARBENES
MESOIONIC
SIGMA DONOR
CLICK REACTION
title_short An Anionic Mesoionic Carbene (anMIC) and its Transformation to Metallo MIC‐Boranes: Synthesis and Properties
title_full An Anionic Mesoionic Carbene (anMIC) and its Transformation to Metallo MIC‐Boranes: Synthesis and Properties
title_fullStr An Anionic Mesoionic Carbene (anMIC) and its Transformation to Metallo MIC‐Boranes: Synthesis and Properties
title_full_unstemmed An Anionic Mesoionic Carbene (anMIC) and its Transformation to Metallo MIC‐Boranes: Synthesis and Properties
title_sort An Anionic Mesoionic Carbene (anMIC) and its Transformation to Metallo MIC‐Boranes: Synthesis and Properties
dc.creator.none.fl_str_mv Rudolf, Richard
Todorovski, Andrej
Lederer, Vera
Neuman, Nicolás Ignacio
Schubert, Hartmut
Sarkar, Biprajit
author Rudolf, Richard
author_facet Rudolf, Richard
Todorovski, Andrej
Lederer, Vera
Neuman, Nicolás Ignacio
Schubert, Hartmut
Sarkar, Biprajit
author_role author
author2 Todorovski, Andrej
Lederer, Vera
Neuman, Nicolás Ignacio
Schubert, Hartmut
Sarkar, Biprajit
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv CARBENES
MESOIONIC
SIGMA DONOR
CLICK REACTION
topic CARBENES
MESOIONIC
SIGMA DONOR
CLICK REACTION
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Neutral mesoionic carbenes (MICs) based on a 1,2,3-triazole core have had a strong impact on various branches of chemistry such as homogeneous catalysis, electrocatalysis, and photochemistry/photophysics. We present here the first general synthesis of anionic mesoionic carbenes (anMICs) based on a 1,2,3-triazole core and a borate backbone. The free anMIC is stable in solution under an inert atmosphere at low temperatures, and can be stored for several weeks. Analysis of donor properties shows that these anMICs are extremely strong σ-donors, bypassing the donor properties of strong donors such as MICs, NHCs, anionic NHCs and N-heterocyclic olefins. The room temperature conversion of the free anMICs leads to three equally interesting compound classes: an amide-coordinated borane based on a MIC-borane backbone, a polymeric triazolide and an amide-coordinated metallo-MIC-borane. The metallo-MIC-borane is an interesting precursor for the synthesis of further amide-coordinated MIC-borane compounds. Quantum chemical calculations have been used to elucidate the mechanism of transformation of the anMICs. Gold(I) complexes of the anMIC ligands are potent catalysts for the hydroamination of alkynes without the need for any additional reagents. We thus introduce three new categories of mesoionic compounds here with potential for different branches of chemistry and beyond.
Fil: Rudolf, Richard. Universitat Stuttgart; Alemania
Fil: Todorovski, Andrej. Universitat Stuttgart; Alemania
Fil: Lederer, Vera. Universitat Stuttgart; Alemania
Fil: Neuman, Nicolás Ignacio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Schubert, Hartmut. Universitat Stuttgart; Alemania
Fil: Sarkar, Biprajit. Universitat Stuttgart; Alemania
description Neutral mesoionic carbenes (MICs) based on a 1,2,3-triazole core have had a strong impact on various branches of chemistry such as homogeneous catalysis, electrocatalysis, and photochemistry/photophysics. We present here the first general synthesis of anionic mesoionic carbenes (anMICs) based on a 1,2,3-triazole core and a borate backbone. The free anMIC is stable in solution under an inert atmosphere at low temperatures, and can be stored for several weeks. Analysis of donor properties shows that these anMICs are extremely strong σ-donors, bypassing the donor properties of strong donors such as MICs, NHCs, anionic NHCs and N-heterocyclic olefins. The room temperature conversion of the free anMICs leads to three equally interesting compound classes: an amide-coordinated borane based on a MIC-borane backbone, a polymeric triazolide and an amide-coordinated metallo-MIC-borane. The metallo-MIC-borane is an interesting precursor for the synthesis of further amide-coordinated MIC-borane compounds. Quantum chemical calculations have been used to elucidate the mechanism of transformation of the anMICs. Gold(I) complexes of the anMIC ligands are potent catalysts for the hydroamination of alkynes without the need for any additional reagents. We thus introduce three new categories of mesoionic compounds here with potential for different branches of chemistry and beyond.
publishDate 2025
dc.date.none.fl_str_mv 2025-01
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/11336/279807
Rudolf, Richard; Todorovski, Andrej; Lederer, Vera; Neuman, Nicolás Ignacio; Schubert, Hartmut; et al.; An Anionic Mesoionic Carbene (anMIC) and its Transformation to Metallo MIC‐Boranes: Synthesis and Properties; Wiley VCH Verlag; Angewandte Chemie; 64; 13; 1-2025; 1-15
1433-7851
CONICET Digital
CONICET
url http://hdl.handle.net/11336/279807
identifier_str_mv Rudolf, Richard; Todorovski, Andrej; Lederer, Vera; Neuman, Nicolás Ignacio; Schubert, Hartmut; et al.; An Anionic Mesoionic Carbene (anMIC) and its Transformation to Metallo MIC‐Boranes: Synthesis and Properties; Wiley VCH Verlag; Angewandte Chemie; 64; 13; 1-2025; 1-15
1433-7851
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://onlinelibrary.wiley.com/doi/10.1002/anie.202422702
info:eu-repo/semantics/altIdentifier/doi/10.1002/anie.202422702
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Wiley VCH Verlag
publisher.none.fl_str_mv Wiley VCH Verlag
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 13.176822

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