Mesoionic Imines (MIIs): Strong Donors and Versatile Ligands for Transition Metals and Main Group Substrates

Autores
Rudolf, Richard; Neuman, Nicolás Ignacio; Walter, Robert R. M.; Ringenberg, Mark. R.; Sarkar, Biprajit
Año de publicación
2022
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We report the synthesis and the reactivity of 1,2,3-triazolin-5-imine type mesoionic imines (MIIs). The MIIs are accessible by a base-mediated cycloaddition between a substituted acetonitrile and an aromatic azide, methylation by established routes and subsequent deprotonation. C=O-stretching frequencies in MII−CO2 and −Rh(CO)2Cl complexes were used to determine the overall donor strength. The MIIs are stronger donors than the N-heterocyclic imines (NHIs). MIIs are excellent ligands for main group elements and transition metals in which they display substituent-induced fluorine-specific interactions and undergo C−H activation. DFT calculations gave insights into the frontier orbitals of the MIIs. The calculations predict a relatively small HOMO–LUMO gap compared to other related ligands. MIIs are potentially able to act as both π-donor and π-acceptor ligands. This report highlights the potential of MIIs to display exciting properties with a huge potential for future development.
Fil: Rudolf, Richard. 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. Universitat Stuttgart; Alemania
Fil: Walter, Robert R. M.. Universitat Stuttgart; Alemania
Fil: Ringenberg, Mark. R.. Universitat Stuttgart; Alemania
Fil: Sarkar, Biprajit. Universitat Stuttgart; Alemania
Materia
C−H ACTIVATION
ELECTRONIC AMBIVALENCE
FLUORINE SPECIFIC INTERACTIONS
MESOIONIC IMINES
STRONG DONORS
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:11336/215943
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Mesoionic Imines (MIIs): Strong Donors and Versatile Ligands for Transition Metals and Main Group SubstratesRudolf, RichardNeuman, Nicolás IgnacioWalter, Robert R. M.Ringenberg, Mark. R.Sarkar, BiprajitC−H ACTIVATIONELECTRONIC AMBIVALENCEFLUORINE SPECIFIC INTERACTIONSMESOIONIC IMINESSTRONG DONORShttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We report the synthesis and the reactivity of 1,2,3-triazolin-5-imine type mesoionic imines (MIIs). The MIIs are accessible by a base-mediated cycloaddition between a substituted acetonitrile and an aromatic azide, methylation by established routes and subsequent deprotonation. C=O-stretching frequencies in MII−CO2 and −Rh(CO)2Cl complexes were used to determine the overall donor strength. The MIIs are stronger donors than the N-heterocyclic imines (NHIs). MIIs are excellent ligands for main group elements and transition metals in which they display substituent-induced fluorine-specific interactions and undergo C−H activation. DFT calculations gave insights into the frontier orbitals of the MIIs. The calculations predict a relatively small HOMO–LUMO gap compared to other related ligands. MIIs are potentially able to act as both π-donor and π-acceptor ligands. This report highlights the potential of MIIs to display exciting properties with a huge potential for future development.Fil: Rudolf, Richard. 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; Argentina. Universitat Stuttgart; AlemaniaFil: Walter, Robert R. M.. Universitat Stuttgart; AlemaniaFil: Ringenberg, Mark. R.. Universitat Stuttgart; AlemaniaFil: Sarkar, Biprajit. Universitat Stuttgart; AlemaniaWiley VCH Verlag2022-03info: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/11336/215943Rudolf, Richard; Neuman, Nicolás Ignacio; Walter, Robert R. M.; Ringenberg, Mark. R.; Sarkar, Biprajit; Mesoionic Imines (MIIs): Strong Donors and Versatile Ligands for Transition Metals and Main Group Substrates; Wiley VCH Verlag; Angewandte Chemie; 61; 25; 3-2022; 1-101433-7851CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/10.1002/anie.202200653info:eu-repo/semantics/altIdentifier/doi/10.1002/anie.202200653info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-10T13:00:37Zoai:ri.conicet.gov.ar:11336/215943instacron: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:34982025-09-10 13:00:38.033CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Mesoionic Imines (MIIs): Strong Donors and Versatile Ligands for Transition Metals and Main Group Substrates
title Mesoionic Imines (MIIs): Strong Donors and Versatile Ligands for Transition Metals and Main Group Substrates
spellingShingle Mesoionic Imines (MIIs): Strong Donors and Versatile Ligands for Transition Metals and Main Group Substrates
Rudolf, Richard
C−H ACTIVATION
ELECTRONIC AMBIVALENCE
FLUORINE SPECIFIC INTERACTIONS
MESOIONIC IMINES
STRONG DONORS
title_short Mesoionic Imines (MIIs): Strong Donors and Versatile Ligands for Transition Metals and Main Group Substrates
title_full Mesoionic Imines (MIIs): Strong Donors and Versatile Ligands for Transition Metals and Main Group Substrates
title_fullStr Mesoionic Imines (MIIs): Strong Donors and Versatile Ligands for Transition Metals and Main Group Substrates
title_full_unstemmed Mesoionic Imines (MIIs): Strong Donors and Versatile Ligands for Transition Metals and Main Group Substrates
title_sort Mesoionic Imines (MIIs): Strong Donors and Versatile Ligands for Transition Metals and Main Group Substrates
dc.creator.none.fl_str_mv Rudolf, Richard
Neuman, Nicolás Ignacio
Walter, Robert R. M.
Ringenberg, Mark. R.
Sarkar, Biprajit
author Rudolf, Richard
author_facet Rudolf, Richard
Neuman, Nicolás Ignacio
Walter, Robert R. M.
Ringenberg, Mark. R.
Sarkar, Biprajit
author_role author
author2 Neuman, Nicolás Ignacio
Walter, Robert R. M.
Ringenberg, Mark. R.
Sarkar, Biprajit
author2_role author
author
author
author
dc.subject.none.fl_str_mv C−H ACTIVATION
ELECTRONIC AMBIVALENCE
FLUORINE SPECIFIC INTERACTIONS
MESOIONIC IMINES
STRONG DONORS
topic C−H ACTIVATION
ELECTRONIC AMBIVALENCE
FLUORINE SPECIFIC INTERACTIONS
MESOIONIC IMINES
STRONG DONORS
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv We report the synthesis and the reactivity of 1,2,3-triazolin-5-imine type mesoionic imines (MIIs). The MIIs are accessible by a base-mediated cycloaddition between a substituted acetonitrile and an aromatic azide, methylation by established routes and subsequent deprotonation. C=O-stretching frequencies in MII−CO2 and −Rh(CO)2Cl complexes were used to determine the overall donor strength. The MIIs are stronger donors than the N-heterocyclic imines (NHIs). MIIs are excellent ligands for main group elements and transition metals in which they display substituent-induced fluorine-specific interactions and undergo C−H activation. DFT calculations gave insights into the frontier orbitals of the MIIs. The calculations predict a relatively small HOMO–LUMO gap compared to other related ligands. MIIs are potentially able to act as both π-donor and π-acceptor ligands. This report highlights the potential of MIIs to display exciting properties with a huge potential for future development.
Fil: Rudolf, Richard. 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. Universitat Stuttgart; Alemania
Fil: Walter, Robert R. M.. Universitat Stuttgart; Alemania
Fil: Ringenberg, Mark. R.. Universitat Stuttgart; Alemania
Fil: Sarkar, Biprajit. Universitat Stuttgart; Alemania
description We report the synthesis and the reactivity of 1,2,3-triazolin-5-imine type mesoionic imines (MIIs). The MIIs are accessible by a base-mediated cycloaddition between a substituted acetonitrile and an aromatic azide, methylation by established routes and subsequent deprotonation. C=O-stretching frequencies in MII−CO2 and −Rh(CO)2Cl complexes were used to determine the overall donor strength. The MIIs are stronger donors than the N-heterocyclic imines (NHIs). MIIs are excellent ligands for main group elements and transition metals in which they display substituent-induced fluorine-specific interactions and undergo C−H activation. DFT calculations gave insights into the frontier orbitals of the MIIs. The calculations predict a relatively small HOMO–LUMO gap compared to other related ligands. MIIs are potentially able to act as both π-donor and π-acceptor ligands. This report highlights the potential of MIIs to display exciting properties with a huge potential for future development.
publishDate 2022
dc.date.none.fl_str_mv 2022-03
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/11336/215943
Rudolf, Richard; Neuman, Nicolás Ignacio; Walter, Robert R. M.; Ringenberg, Mark. R.; Sarkar, Biprajit; Mesoionic Imines (MIIs): Strong Donors and Versatile Ligands for Transition Metals and Main Group Substrates; Wiley VCH Verlag; Angewandte Chemie; 61; 25; 3-2022; 1-10
1433-7851
CONICET Digital
CONICET
url http://hdl.handle.net/11336/215943
identifier_str_mv Rudolf, Richard; Neuman, Nicolás Ignacio; Walter, Robert R. M.; Ringenberg, Mark. R.; Sarkar, Biprajit; Mesoionic Imines (MIIs): Strong Donors and Versatile Ligands for Transition Metals and Main Group Substrates; Wiley VCH Verlag; Angewandte Chemie; 61; 25; 3-2022; 1-10
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.202200653
info:eu-repo/semantics/altIdentifier/doi/10.1002/anie.202200653
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
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 12.993085

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