Aluminium porphyrins catalyse the hydrogenation of CO 2 with H 2

Autores
Kumar, Nitin; Gastelu, Gabriela; Zábranský, Martin; Kukla, Jaroslav; Uranga, Jorge Gustavo; Hulla, Martin
Año de publicación
2024
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Boron-based frustrated Lewis pairs (FLPs) have become well-established catalysts for the hydrogenation of a wide range of functional groups. Conversely, aluminium-based FLP hydrogenation catalysts are less common, especially for CO2 reduction. They are mostly confined to the hydrogenation of imines, alkenes, and alkynes even though aluminium is much more abundant than boron and forms structurally related compounds. Moreover, aluminium forms penta- and hexa-coordinated complexes, which remain untested in FLP hydrogenation catalysis. Herein, we demonstrate that cationic, hexa-coordinated diaqua-meso-tetraphenylporphyrin aluminium complexes [Al(TPP)(OH2)2]X and [Al(t BuTPP)(OH2)2]X (X = Cl−, OTf−, ClO4 −) form FLPs with nitrogen bases, activate H2, and reductively couple CO2 to amines, yielding N-formylamines and water. Our experimental results and DFT analysis indicate that H2 activation involves the formation of an FLP, base-promoted CO2 reduction and formate salt elimination from the FLP, as proposed for transition metal-catalyzed N-formylations. These similarities in the reaction mechanism and structure of aluminium complexes brings Al-based FLPs closer to transition metal catalysis and may enable us to apply this knowledge to ligand design to enhance main group metalpromoted hydrogenations.
Fil: Kumar, Nitin. Charles University; Portugal
Fil: Gastelu, Gabriela. 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: Zábranský, Martin. Charles University; Puerto Rico
Fil: Kukla, Jaroslav. Charles University; Portugal
Fil: Uranga, Jorge Gustavo. 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: Hulla, Martin. Charles University; Portugal
Materia
CO2
Frsutrated Lewis Pairs
Aluminium
Hydrogenation
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/263991
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/263991
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Aluminium porphyrins catalyse the hydrogenation of CO 2 with H 2Kumar, NitinGastelu, GabrielaZábranský, MartinKukla, JaroslavUranga, Jorge GustavoHulla, MartinCO2Frsutrated Lewis PairsAluminiumHydrogenationhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Boron-based frustrated Lewis pairs (FLPs) have become well-established catalysts for the hydrogenation of a wide range of functional groups. Conversely, aluminium-based FLP hydrogenation catalysts are less common, especially for CO2 reduction. They are mostly confined to the hydrogenation of imines, alkenes, and alkynes even though aluminium is much more abundant than boron and forms structurally related compounds. Moreover, aluminium forms penta- and hexa-coordinated complexes, which remain untested in FLP hydrogenation catalysis. Herein, we demonstrate that cationic, hexa-coordinated diaqua-meso-tetraphenylporphyrin aluminium complexes [Al(TPP)(OH2)2]X and [Al(t BuTPP)(OH2)2]X (X = Cl−, OTf−, ClO4 −) form FLPs with nitrogen bases, activate H2, and reductively couple CO2 to amines, yielding N-formylamines and water. Our experimental results and DFT analysis indicate that H2 activation involves the formation of an FLP, base-promoted CO2 reduction and formate salt elimination from the FLP, as proposed for transition metal-catalyzed N-formylations. These similarities in the reaction mechanism and structure of aluminium complexes brings Al-based FLPs closer to transition metal catalysis and may enable us to apply this knowledge to ligand design to enhance main group metalpromoted hydrogenations.Fil: Kumar, Nitin. Charles University; PortugalFil: Gastelu, Gabriela. 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: Zábranský, Martin. Charles University; Puerto RicoFil: Kukla, Jaroslav. Charles University; PortugalFil: Uranga, Jorge Gustavo. 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: Hulla, Martin. Charles University; PortugalRoyal Society of Chemistry2024-11info: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/11336/263991Kumar, Nitin; Gastelu, Gabriela; Zábranský, Martin; Kukla, Jaroslav; Uranga, Jorge Gustavo; et al.; Aluminium porphyrins catalyse the hydrogenation of CO 2 with H 2; Royal Society of Chemistry; Chemical Science; 15; 48; 11-2024; 20573-205812041-6520CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://xlink.rsc.org/?DOI=D4SC03665Dinfo:eu-repo/semantics/altIdentifier/doi/10.1039/D4SC03665Dinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:02:52Zoai:ri.conicet.gov.ar:11336/263991instacron: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:34982025-10-22 11:02:52.556CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Aluminium porphyrins catalyse the hydrogenation of CO 2 with H 2
title Aluminium porphyrins catalyse the hydrogenation of CO 2 with H 2
spellingShingle Aluminium porphyrins catalyse the hydrogenation of CO 2 with H 2
Kumar, Nitin
CO2
Frsutrated Lewis Pairs
Aluminium
Hydrogenation
title_short Aluminium porphyrins catalyse the hydrogenation of CO 2 with H 2
title_full Aluminium porphyrins catalyse the hydrogenation of CO 2 with H 2
title_fullStr Aluminium porphyrins catalyse the hydrogenation of CO 2 with H 2
title_full_unstemmed Aluminium porphyrins catalyse the hydrogenation of CO 2 with H 2
title_sort Aluminium porphyrins catalyse the hydrogenation of CO 2 with H 2
dc.creator.none.fl_str_mv Kumar, Nitin
Gastelu, Gabriela
Zábranský, Martin
Kukla, Jaroslav
Uranga, Jorge Gustavo
Hulla, Martin
author Kumar, Nitin
author_facet Kumar, Nitin
Gastelu, Gabriela
Zábranský, Martin
Kukla, Jaroslav
Uranga, Jorge Gustavo
Hulla, Martin
author_role author
author2 Gastelu, Gabriela
Zábranský, Martin
Kukla, Jaroslav
Uranga, Jorge Gustavo
Hulla, Martin
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv CO2
Frsutrated Lewis Pairs
Aluminium
Hydrogenation
topic CO2
Frsutrated Lewis Pairs
Aluminium
Hydrogenation
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Boron-based frustrated Lewis pairs (FLPs) have become well-established catalysts for the hydrogenation of a wide range of functional groups. Conversely, aluminium-based FLP hydrogenation catalysts are less common, especially for CO2 reduction. They are mostly confined to the hydrogenation of imines, alkenes, and alkynes even though aluminium is much more abundant than boron and forms structurally related compounds. Moreover, aluminium forms penta- and hexa-coordinated complexes, which remain untested in FLP hydrogenation catalysis. Herein, we demonstrate that cationic, hexa-coordinated diaqua-meso-tetraphenylporphyrin aluminium complexes [Al(TPP)(OH2)2]X and [Al(t BuTPP)(OH2)2]X (X = Cl−, OTf−, ClO4 −) form FLPs with nitrogen bases, activate H2, and reductively couple CO2 to amines, yielding N-formylamines and water. Our experimental results and DFT analysis indicate that H2 activation involves the formation of an FLP, base-promoted CO2 reduction and formate salt elimination from the FLP, as proposed for transition metal-catalyzed N-formylations. These similarities in the reaction mechanism and structure of aluminium complexes brings Al-based FLPs closer to transition metal catalysis and may enable us to apply this knowledge to ligand design to enhance main group metalpromoted hydrogenations.
Fil: Kumar, Nitin. Charles University; Portugal
Fil: Gastelu, Gabriela. 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: Zábranský, Martin. Charles University; Puerto Rico
Fil: Kukla, Jaroslav. Charles University; Portugal
Fil: Uranga, Jorge Gustavo. 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: Hulla, Martin. Charles University; Portugal
description Boron-based frustrated Lewis pairs (FLPs) have become well-established catalysts for the hydrogenation of a wide range of functional groups. Conversely, aluminium-based FLP hydrogenation catalysts are less common, especially for CO2 reduction. They are mostly confined to the hydrogenation of imines, alkenes, and alkynes even though aluminium is much more abundant than boron and forms structurally related compounds. Moreover, aluminium forms penta- and hexa-coordinated complexes, which remain untested in FLP hydrogenation catalysis. Herein, we demonstrate that cationic, hexa-coordinated diaqua-meso-tetraphenylporphyrin aluminium complexes [Al(TPP)(OH2)2]X and [Al(t BuTPP)(OH2)2]X (X = Cl−, OTf−, ClO4 −) form FLPs with nitrogen bases, activate H2, and reductively couple CO2 to amines, yielding N-formylamines and water. Our experimental results and DFT analysis indicate that H2 activation involves the formation of an FLP, base-promoted CO2 reduction and formate salt elimination from the FLP, as proposed for transition metal-catalyzed N-formylations. These similarities in the reaction mechanism and structure of aluminium complexes brings Al-based FLPs closer to transition metal catalysis and may enable us to apply this knowledge to ligand design to enhance main group metalpromoted hydrogenations.
publishDate 2024
dc.date.none.fl_str_mv 2024-11
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/11336/263991
Kumar, Nitin; Gastelu, Gabriela; Zábranský, Martin; Kukla, Jaroslav; Uranga, Jorge Gustavo; et al.; Aluminium porphyrins catalyse the hydrogenation of CO 2 with H 2; Royal Society of Chemistry; Chemical Science; 15; 48; 11-2024; 20573-20581
2041-6520
CONICET Digital
CONICET
url http://hdl.handle.net/11336/263991
identifier_str_mv Kumar, Nitin; Gastelu, Gabriela; Zábranský, Martin; Kukla, Jaroslav; Uranga, Jorge Gustavo; et al.; Aluminium porphyrins catalyse the hydrogenation of CO 2 with H 2; Royal Society of Chemistry; Chemical Science; 15; 48; 11-2024; 20573-20581
2041-6520
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://xlink.rsc.org/?DOI=D4SC03665D
info:eu-repo/semantics/altIdentifier/doi/10.1039/D4SC03665D
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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 12.982451

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