Isomerization Reactions in Anionic Mesoionic Carbene‐Borates and Control of Properties and Reactivities in the resulting CoII Complexes through Agostic Interactions

Autores
Stubbe, Jessica; Neuman, Nicolás Ignacio; Mclellan, Ross; Sommer, Michael; Nößler, Maite; Beerhues, Julia; Mulvey, Robert; Sarkar, Biprajit
Año de publicación
2020
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We present herein anionic borate-based bi-mesoionic carbene compounds of the 1,2,3-triazol-4-ylidene type that undergo C−N isomerization reactions. The isomerized compounds are excellent ligands for CoII centers. Strong agostic interactions with the “C−H”-groups of the cyclohexyl substituents result in an unusual low-spin square planar CoII complex, which is unreactive towards external substrates. Such agostic interactions are absent in the complex with phenyl substituents on the borate backbone. This complex displays a high-spin tetrahedral CoII center, which is reactive towards external substrates including dioxygen. To the best of our knowledge, this is also the first investigation of agostic interactions through single-crystal EPR spectroscopy. We conclusively show here that the structure and properties of these CoII complexes can be strongly influenced through interactions in the secondary coordination sphere. Additionally, we unravel a unique ligand rearrangement for these classes of anionic mesoionic carbene-based ligands.
Fil: Stubbe, Jessica. Freie Universität Berlin; 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: Mclellan, Ross. Freie Universität Berlin; Alemania
Fil: Sommer, Michael. Freie Universität Berlin; Alemania
Fil: Nößler, Maite. Freie Universität Berlin; Alemania
Fil: Beerhues, Julia. Universitat Stuttgart; Alemania
Fil: Mulvey, Robert. Freie Universität Berlin; Alemania
Fil: Sarkar, Biprajit. Universitat Stuttgart; Alemania
Materia
COBALT
LIGAND REARRANGEMENT
MESOIONIC CARBENE
REACTIVITY
SPIN STATE
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:11336/127930
Acceder
id CONICETDig_8b072a96e0047be42ce956d233d882cc
oai_identifier_str oai:ri.conicet.gov.ar:11336/127930
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Isomerization Reactions in Anionic Mesoionic Carbene‐Borates and Control of Properties and Reactivities in the resulting CoII Complexes through Agostic InteractionsStubbe, JessicaNeuman, Nicolás IgnacioMclellan, RossSommer, MichaelNößler, MaiteBeerhues, JuliaMulvey, RobertSarkar, BiprajitCOBALTLIGAND REARRANGEMENTMESOIONIC CARBENEREACTIVITYSPIN STATEhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We present herein anionic borate-based bi-mesoionic carbene compounds of the 1,2,3-triazol-4-ylidene type that undergo C−N isomerization reactions. The isomerized compounds are excellent ligands for CoII centers. Strong agostic interactions with the “C−H”-groups of the cyclohexyl substituents result in an unusual low-spin square planar CoII complex, which is unreactive towards external substrates. Such agostic interactions are absent in the complex with phenyl substituents on the borate backbone. This complex displays a high-spin tetrahedral CoII center, which is reactive towards external substrates including dioxygen. To the best of our knowledge, this is also the first investigation of agostic interactions through single-crystal EPR spectroscopy. We conclusively show here that the structure and properties of these CoII complexes can be strongly influenced through interactions in the secondary coordination sphere. Additionally, we unravel a unique ligand rearrangement for these classes of anionic mesoionic carbene-based ligands.Fil: Stubbe, Jessica. Freie Universität Berlin; 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: Mclellan, Ross. Freie Universität Berlin; AlemaniaFil: Sommer, Michael. Freie Universität Berlin; AlemaniaFil: Nößler, Maite. Freie Universität Berlin; AlemaniaFil: Beerhues, Julia. Universitat Stuttgart; AlemaniaFil: Mulvey, Robert. Freie Universität Berlin; AlemaniaFil: Sarkar, Biprajit. Universitat Stuttgart; AlemaniaWiley VCH Verlag2020-10info: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/11336/127930Stubbe, Jessica; Neuman, Nicolás Ignacio; Mclellan, Ross; Sommer, Michael; Nößler, Maite; et al.; Isomerization Reactions in Anionic Mesoionic Carbene‐Borates and Control of Properties and Reactivities in the resulting CoII Complexes through Agostic Interactions; Wiley VCH Verlag; Angewandte Chemie; 60; 1; 10-2020; 499-5061433-7851CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/10.1002/anie.202013376info:eu-repo/semantics/altIdentifier/doi/10.1002/anie.202013376info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:50:00Zoai:ri.conicet.gov.ar:11336/127930instacron: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:34982025-09-03 09:50:00.971CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Isomerization Reactions in Anionic Mesoionic Carbene‐Borates and Control of Properties and Reactivities in the resulting CoII Complexes through Agostic Interactions
title Isomerization Reactions in Anionic Mesoionic Carbene‐Borates and Control of Properties and Reactivities in the resulting CoII Complexes through Agostic Interactions
spellingShingle Isomerization Reactions in Anionic Mesoionic Carbene‐Borates and Control of Properties and Reactivities in the resulting CoII Complexes through Agostic Interactions
Stubbe, Jessica
COBALT
LIGAND REARRANGEMENT
MESOIONIC CARBENE
REACTIVITY
SPIN STATE
title_short Isomerization Reactions in Anionic Mesoionic Carbene‐Borates and Control of Properties and Reactivities in the resulting CoII Complexes through Agostic Interactions
title_full Isomerization Reactions in Anionic Mesoionic Carbene‐Borates and Control of Properties and Reactivities in the resulting CoII Complexes through Agostic Interactions
title_fullStr Isomerization Reactions in Anionic Mesoionic Carbene‐Borates and Control of Properties and Reactivities in the resulting CoII Complexes through Agostic Interactions
title_full_unstemmed Isomerization Reactions in Anionic Mesoionic Carbene‐Borates and Control of Properties and Reactivities in the resulting CoII Complexes through Agostic Interactions
title_sort Isomerization Reactions in Anionic Mesoionic Carbene‐Borates and Control of Properties and Reactivities in the resulting CoII Complexes through Agostic Interactions
dc.creator.none.fl_str_mv Stubbe, Jessica
Neuman, Nicolás Ignacio
Mclellan, Ross
Sommer, Michael
Nößler, Maite
Beerhues, Julia
Mulvey, Robert
Sarkar, Biprajit
author Stubbe, Jessica
author_facet Stubbe, Jessica
Neuman, Nicolás Ignacio
Mclellan, Ross
Sommer, Michael
Nößler, Maite
Beerhues, Julia
Mulvey, Robert
Sarkar, Biprajit
author_role author
author2 Neuman, Nicolás Ignacio
Mclellan, Ross
Sommer, Michael
Nößler, Maite
Beerhues, Julia
Mulvey, Robert
Sarkar, Biprajit
author2_role author
author
author
author
author
author
author
dc.subject.none.fl_str_mv COBALT
LIGAND REARRANGEMENT
MESOIONIC CARBENE
REACTIVITY
SPIN STATE
topic COBALT
LIGAND REARRANGEMENT
MESOIONIC CARBENE
REACTIVITY
SPIN STATE
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 present herein anionic borate-based bi-mesoionic carbene compounds of the 1,2,3-triazol-4-ylidene type that undergo C−N isomerization reactions. The isomerized compounds are excellent ligands for CoII centers. Strong agostic interactions with the “C−H”-groups of the cyclohexyl substituents result in an unusual low-spin square planar CoII complex, which is unreactive towards external substrates. Such agostic interactions are absent in the complex with phenyl substituents on the borate backbone. This complex displays a high-spin tetrahedral CoII center, which is reactive towards external substrates including dioxygen. To the best of our knowledge, this is also the first investigation of agostic interactions through single-crystal EPR spectroscopy. We conclusively show here that the structure and properties of these CoII complexes can be strongly influenced through interactions in the secondary coordination sphere. Additionally, we unravel a unique ligand rearrangement for these classes of anionic mesoionic carbene-based ligands.
Fil: Stubbe, Jessica. Freie Universität Berlin; 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: Mclellan, Ross. Freie Universität Berlin; Alemania
Fil: Sommer, Michael. Freie Universität Berlin; Alemania
Fil: Nößler, Maite. Freie Universität Berlin; Alemania
Fil: Beerhues, Julia. Universitat Stuttgart; Alemania
Fil: Mulvey, Robert. Freie Universität Berlin; Alemania
Fil: Sarkar, Biprajit. Universitat Stuttgart; Alemania
description We present herein anionic borate-based bi-mesoionic carbene compounds of the 1,2,3-triazol-4-ylidene type that undergo C−N isomerization reactions. The isomerized compounds are excellent ligands for CoII centers. Strong agostic interactions with the “C−H”-groups of the cyclohexyl substituents result in an unusual low-spin square planar CoII complex, which is unreactive towards external substrates. Such agostic interactions are absent in the complex with phenyl substituents on the borate backbone. This complex displays a high-spin tetrahedral CoII center, which is reactive towards external substrates including dioxygen. To the best of our knowledge, this is also the first investigation of agostic interactions through single-crystal EPR spectroscopy. We conclusively show here that the structure and properties of these CoII complexes can be strongly influenced through interactions in the secondary coordination sphere. Additionally, we unravel a unique ligand rearrangement for these classes of anionic mesoionic carbene-based ligands.
publishDate 2020
dc.date.none.fl_str_mv 2020-10
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/11336/127930
Stubbe, Jessica; Neuman, Nicolás Ignacio; Mclellan, Ross; Sommer, Michael; Nößler, Maite; et al.; Isomerization Reactions in Anionic Mesoionic Carbene‐Borates and Control of Properties and Reactivities in the resulting CoII Complexes through Agostic Interactions; Wiley VCH Verlag; Angewandte Chemie; 60; 1; 10-2020; 499-506
1433-7851
CONICET Digital
CONICET
url http://hdl.handle.net/11336/127930
identifier_str_mv Stubbe, Jessica; Neuman, Nicolás Ignacio; Mclellan, Ross; Sommer, Michael; Nößler, Maite; et al.; Isomerization Reactions in Anionic Mesoionic Carbene‐Borates and Control of Properties and Reactivities in the resulting CoII Complexes through Agostic Interactions; Wiley VCH Verlag; Angewandte Chemie; 60; 1; 10-2020; 499-506
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.202013376
info:eu-repo/semantics/altIdentifier/doi/10.1002/anie.202013376
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
_version_ 1842269007857582080
score 12.885934

Publicaciones similares