Trivalent Metal Lewis Acids Activate CO 2 in Transfer Hydrogenations

Autores
Paparakis, Alexandros; Mena, Leandro Daniel; Saha, Pritha; Das, Krishna Mohan; Shirwani, Daniel; Uranga, Jorge Gustavo; Hulla, Martin
Año de publicación
2025
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Using γ-terpinene as a bio-derived H2 surrogate, trivalent metal MX3 (M = Al, Ga, In, Yb, X = Cl, OTf ) Lewis acids (LAs) catalyze CO2 hydrogenation to formate, yielding p-cymene as the by-product. The resulting formate produces up to 91% N-formamides in tandem hydrogenation-coupling reactions and up to 95% heterocycles, including azoles, via further in situ transfer formylation to ortho-substituted anilines and cyclization at 130 °C and 4 bar. But In(OTf )3 and a Lewis base fail to abstract a hydride from γ-terpinene. Unlike other LAs and transfer hydrogenation catalysts that induce hydride abstraction from 1,4-cyclohexadiene(s) over B(C6F5)3, alkali earth or noble metals, MX3 LAs activate CO2, so CO2 can directly accept a hydride from γ-terpinene during formate synthesis, as shown by density functional theory calculations. This triple role of MX3 LAs in promoting (1) CO2 activation, (2) tandem coupling reactions, and (3) transfer formylation at low pressure paves the way for sustainable CO2 hydrogenation processes, leveraging bio-derived H2 surrogates to develop efficient carbon capture and utilization systems and to synthesize valuable compounds from renewable feedstocks.
Fil: Paparakis, Alexandros. Charles Darwin University. School of Environmental Research; Australia
Fil: Mena, Leandro Daniel. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Química Orgánica; Argentina. 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: Saha, Pritha. Charles Darwin University. School of Environmental Research; Australia
Fil: Das, Krishna Mohan. Charles Darwin University. School of Environmental Research; Australia
Fil: Shirwani, Daniel. Charles Darwin University. School of Environmental Research; Australia
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 Darwin University. School of Environmental Research; Australia
Materia
CO2
reducción
Indio
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:11336/279932
Acceder
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network_acronym_str CONICETDig
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network_name_str CONICET Digital (CONICET)
spelling Trivalent Metal Lewis Acids Activate CO 2 in Transfer HydrogenationsPaparakis, AlexandrosMena, Leandro DanielSaha, PrithaDas, Krishna MohanShirwani, DanielUranga, Jorge GustavoHulla, MartinCO2reducciónIndiohttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Using γ-terpinene as a bio-derived H2 surrogate, trivalent metal MX3 (M = Al, Ga, In, Yb, X = Cl, OTf ) Lewis acids (LAs) catalyze CO2 hydrogenation to formate, yielding p-cymene as the by-product. The resulting formate produces up to 91% N-formamides in tandem hydrogenation-coupling reactions and up to 95% heterocycles, including azoles, via further in situ transfer formylation to ortho-substituted anilines and cyclization at 130 °C and 4 bar. But In(OTf )3 and a Lewis base fail to abstract a hydride from γ-terpinene. Unlike other LAs and transfer hydrogenation catalysts that induce hydride abstraction from 1,4-cyclohexadiene(s) over B(C6F5)3, alkali earth or noble metals, MX3 LAs activate CO2, so CO2 can directly accept a hydride from γ-terpinene during formate synthesis, as shown by density functional theory calculations. This triple role of MX3 LAs in promoting (1) CO2 activation, (2) tandem coupling reactions, and (3) transfer formylation at low pressure paves the way for sustainable CO2 hydrogenation processes, leveraging bio-derived H2 surrogates to develop efficient carbon capture and utilization systems and to synthesize valuable compounds from renewable feedstocks.Fil: Paparakis, Alexandros. Charles Darwin University. School of Environmental Research; AustraliaFil: Mena, Leandro Daniel. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Química Orgánica; Argentina. 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: Saha, Pritha. Charles Darwin University. School of Environmental Research; AustraliaFil: Das, Krishna Mohan. Charles Darwin University. School of Environmental Research; AustraliaFil: Shirwani, Daniel. Charles Darwin University. School of Environmental Research; AustraliaFil: 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 Darwin University. School of Environmental Research; AustraliaWiley VCH Verlag2025-07info: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/11336/279932Paparakis, Alexandros; Mena, Leandro Daniel; Saha, Pritha; Das, Krishna Mohan; Shirwani, Daniel; et al.; Trivalent Metal Lewis Acids Activate CO 2 in Transfer Hydrogenations; Wiley VCH Verlag; Chemsuschem; 18; 16; 7-2025; 1-51864-5631CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cssc.202500629info:eu-repo/semantics/altIdentifier/doi/10.1002/cssc.202500629info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2026-02-26T10:10:00Zoai:ri.conicet.gov.ar:11336/279932instacron: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 10:10:01.008CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Trivalent Metal Lewis Acids Activate CO 2 in Transfer Hydrogenations
title Trivalent Metal Lewis Acids Activate CO 2 in Transfer Hydrogenations
spellingShingle Trivalent Metal Lewis Acids Activate CO 2 in Transfer Hydrogenations
Paparakis, Alexandros
CO2
reducción
Indio
title_short Trivalent Metal Lewis Acids Activate CO 2 in Transfer Hydrogenations
title_full Trivalent Metal Lewis Acids Activate CO 2 in Transfer Hydrogenations
title_fullStr Trivalent Metal Lewis Acids Activate CO 2 in Transfer Hydrogenations
title_full_unstemmed Trivalent Metal Lewis Acids Activate CO 2 in Transfer Hydrogenations
title_sort Trivalent Metal Lewis Acids Activate CO 2 in Transfer Hydrogenations
dc.creator.none.fl_str_mv Paparakis, Alexandros
Mena, Leandro Daniel
Saha, Pritha
Das, Krishna Mohan
Shirwani, Daniel
Uranga, Jorge Gustavo
Hulla, Martin
author Paparakis, Alexandros
author_facet Paparakis, Alexandros
Mena, Leandro Daniel
Saha, Pritha
Das, Krishna Mohan
Shirwani, Daniel
Uranga, Jorge Gustavo
Hulla, Martin
author_role author
author2 Mena, Leandro Daniel
Saha, Pritha
Das, Krishna Mohan
Shirwani, Daniel
Uranga, Jorge Gustavo
Hulla, Martin
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv CO2
reducción
Indio
topic CO2
reducción
Indio
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Using γ-terpinene as a bio-derived H2 surrogate, trivalent metal MX3 (M = Al, Ga, In, Yb, X = Cl, OTf ) Lewis acids (LAs) catalyze CO2 hydrogenation to formate, yielding p-cymene as the by-product. The resulting formate produces up to 91% N-formamides in tandem hydrogenation-coupling reactions and up to 95% heterocycles, including azoles, via further in situ transfer formylation to ortho-substituted anilines and cyclization at 130 °C and 4 bar. But In(OTf )3 and a Lewis base fail to abstract a hydride from γ-terpinene. Unlike other LAs and transfer hydrogenation catalysts that induce hydride abstraction from 1,4-cyclohexadiene(s) over B(C6F5)3, alkali earth or noble metals, MX3 LAs activate CO2, so CO2 can directly accept a hydride from γ-terpinene during formate synthesis, as shown by density functional theory calculations. This triple role of MX3 LAs in promoting (1) CO2 activation, (2) tandem coupling reactions, and (3) transfer formylation at low pressure paves the way for sustainable CO2 hydrogenation processes, leveraging bio-derived H2 surrogates to develop efficient carbon capture and utilization systems and to synthesize valuable compounds from renewable feedstocks.
Fil: Paparakis, Alexandros. Charles Darwin University. School of Environmental Research; Australia
Fil: Mena, Leandro Daniel. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Química Orgánica; Argentina. 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: Saha, Pritha. Charles Darwin University. School of Environmental Research; Australia
Fil: Das, Krishna Mohan. Charles Darwin University. School of Environmental Research; Australia
Fil: Shirwani, Daniel. Charles Darwin University. School of Environmental Research; Australia
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 Darwin University. School of Environmental Research; Australia
description Using γ-terpinene as a bio-derived H2 surrogate, trivalent metal MX3 (M = Al, Ga, In, Yb, X = Cl, OTf ) Lewis acids (LAs) catalyze CO2 hydrogenation to formate, yielding p-cymene as the by-product. The resulting formate produces up to 91% N-formamides in tandem hydrogenation-coupling reactions and up to 95% heterocycles, including azoles, via further in situ transfer formylation to ortho-substituted anilines and cyclization at 130 °C and 4 bar. But In(OTf )3 and a Lewis base fail to abstract a hydride from γ-terpinene. Unlike other LAs and transfer hydrogenation catalysts that induce hydride abstraction from 1,4-cyclohexadiene(s) over B(C6F5)3, alkali earth or noble metals, MX3 LAs activate CO2, so CO2 can directly accept a hydride from γ-terpinene during formate synthesis, as shown by density functional theory calculations. This triple role of MX3 LAs in promoting (1) CO2 activation, (2) tandem coupling reactions, and (3) transfer formylation at low pressure paves the way for sustainable CO2 hydrogenation processes, leveraging bio-derived H2 surrogates to develop efficient carbon capture and utilization systems and to synthesize valuable compounds from renewable feedstocks.
publishDate 2025
dc.date.none.fl_str_mv 2025-07
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/11336/279932
Paparakis, Alexandros; Mena, Leandro Daniel; Saha, Pritha; Das, Krishna Mohan; Shirwani, Daniel; et al.; Trivalent Metal Lewis Acids Activate CO 2 in Transfer Hydrogenations; Wiley VCH Verlag; Chemsuschem; 18; 16; 7-2025; 1-5
1864-5631
CONICET Digital
CONICET
url http://hdl.handle.net/11336/279932
identifier_str_mv Paparakis, Alexandros; Mena, Leandro Daniel; Saha, Pritha; Das, Krishna Mohan; Shirwani, Daniel; et al.; Trivalent Metal Lewis Acids Activate CO 2 in Transfer Hydrogenations; Wiley VCH Verlag; Chemsuschem; 18; 16; 7-2025; 1-5
1864-5631
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://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cssc.202500629
info:eu-repo/semantics/altIdentifier/doi/10.1002/cssc.202500629
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 13.176822

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