Preparation and degradation of rhodium and iridium diolefin catalysts for the acceptorless and base-free dehydrogenation of secondary alcohols

Rhodium and iridium diolefin catalysts for the acceptorless and base-free dehydrogenation of secondary alcohols have been prepared, and their degradation has been investigated, during the study of the reactivity of the dimers [M(μ-Cl)(η4-C8H12)]2 (M = Rh (1), Ir (2)) and [M(μ-OH)(η4-C8H12)]2 (M = Rh...

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Autores: Buil, María L., Collado, Alba, Esteruelas, Miguel A., Gómez-Gallego, Mar, Izquierdo, Susana, Nicasio, Antonio I., Oñate, Enrique, Sierra, Miguel A.
Formato: artículo
Estado:Versión publicada
Fecha de publicación:2021
País:España
Recursos:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/237746
Acesso em linha:http://hdl.handle.net/10261/237746
Access Level:acceso abierto
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spelling Preparation and degradation of rhodium and iridium diolefin catalysts for the acceptorless and base-free dehydrogenation of secondary alcoholsBuil, María L.Collado, AlbaEsteruelas, Miguel A.Gómez-Gallego, MarIzquierdo, SusanaNicasio, Antonio I.Oñate, EnriqueSierra, Miguel A.Rhodium and iridium diolefin catalysts for the acceptorless and base-free dehydrogenation of secondary alcohols have been prepared, and their degradation has been investigated, during the study of the reactivity of the dimers [M(μ-Cl)(η4-C8H12)]2 (M = Rh (1), Ir (2)) and [M(μ-OH)(η4-C8H12)]2 (M = Rh (3), Ir (4)) with 1,3-bis(6′-methyl-2′-pyridylimino)isoindoline (HBMePHI). Complex 1 reacts with HBMePHI, in dichloromethane, to afford equilibrium mixtures of 1, the mononuclear derivative RhCl(η4-C8H12){κ1-Npy-(HBMePHI)} (5), and the binuclear species [RhCl(η4-C8H12)]2{μ-Npy,Npy-(HBMePHI)} (6). Under the same conditions, complex 2 affords the iridium counterparts IrCl(η4-C8H12){κ1-Npy-(HBMePHI)} (7) and [IrCl(η4-C8H12)]2{μ-Npy,Npy-(HBMePHI)} (8). In contrast to chloride, one of the hydroxide groups of 3 and 4 promotes the deprotonation of HBMePHI to give [M(η4-C8H12)]2(μ-OH){μ-Npy,Niso-(BMePHI)} (M = Rh (9), Ir (10)), which are efficient precatalysts for the acceptorless and base-free dehydrogenation of secondary alcohols. In the presence of KOtBu, the [BMePHI]− ligand undergoes three different degradations: alcoholysis of an exocyclic isoindoline-N double bond, alcoholysis of a pyridyl-N bond, and opening of the five-membered ring of the isoindoline core.Financial support from the MCI, projects CTQ2017-82935-P, PID2019-108429RB-I00, and RED2018-102387-T, the Gobierno de Aragón (Group E06_17R), Fundación Ramón Areces (XVIII Concurso Nacional de Ayudas a la Investigación en Ciencias de la Vida y de la Materia CIVP18A3938), Fondo Europeo de Desarrollo Regional (FEDER), and the European Social Fund (FSE) is acknowledged. A.I.N. and A.C. thank the MINECO (Spain) for a predoctoral fellowship and Juan de la Cierva-Incorporación Fellowship, respectively.Peer reviewedAmerican Chemical SocietyMinisterio de Ciencia, Innovación y Universidades (España)Agencia Estatal de Investigación (España)Gobierno de AragónEuropean CommissionFundación Ramón ArecesMinisterio de Economía y Competitividad (España)Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202120212021info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionhttp://hdl.handle.net/10261/237746reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2017-82935-Pinfo:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-108429RB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/RED2018-102387-Thttps://doi.org/10.1021/acs.organomet.1c00068Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/2377462026-05-22T06:33:51Z
dc.title.none.fl_str_mv Preparation and degradation of rhodium and iridium diolefin catalysts for the acceptorless and base-free dehydrogenation of secondary alcohols
title Preparation and degradation of rhodium and iridium diolefin catalysts for the acceptorless and base-free dehydrogenation of secondary alcohols
spellingShingle Preparation and degradation of rhodium and iridium diolefin catalysts for the acceptorless and base-free dehydrogenation of secondary alcohols
Buil, María L.
title_short Preparation and degradation of rhodium and iridium diolefin catalysts for the acceptorless and base-free dehydrogenation of secondary alcohols
title_full Preparation and degradation of rhodium and iridium diolefin catalysts for the acceptorless and base-free dehydrogenation of secondary alcohols
title_fullStr Preparation and degradation of rhodium and iridium diolefin catalysts for the acceptorless and base-free dehydrogenation of secondary alcohols
title_full_unstemmed Preparation and degradation of rhodium and iridium diolefin catalysts for the acceptorless and base-free dehydrogenation of secondary alcohols
title_sort Preparation and degradation of rhodium and iridium diolefin catalysts for the acceptorless and base-free dehydrogenation of secondary alcohols
dc.creator.none.fl_str_mv Buil, María L.
Collado, Alba
Esteruelas, Miguel A.
Gómez-Gallego, Mar
Izquierdo, Susana
Nicasio, Antonio I.
Oñate, Enrique
Sierra, Miguel A.
author Buil, María L.
author_facet Buil, María L.
Collado, Alba
Esteruelas, Miguel A.
Gómez-Gallego, Mar
Izquierdo, Susana
Nicasio, Antonio I.
Oñate, Enrique
Sierra, Miguel A.
author_role author
author2 Collado, Alba
Esteruelas, Miguel A.
Gómez-Gallego, Mar
Izquierdo, Susana
Nicasio, Antonio I.
Oñate, Enrique
Sierra, Miguel A.
author2_role author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Ciencia, Innovación y Universidades (España)
Agencia Estatal de Investigación (España)
Gobierno de Aragón
European Commission
Fundación Ramón Areces
Ministerio de Economía y Competitividad (España)
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description Rhodium and iridium diolefin catalysts for the acceptorless and base-free dehydrogenation of secondary alcohols have been prepared, and their degradation has been investigated, during the study of the reactivity of the dimers [M(μ-Cl)(η4-C8H12)]2 (M = Rh (1), Ir (2)) and [M(μ-OH)(η4-C8H12)]2 (M = Rh (3), Ir (4)) with 1,3-bis(6′-methyl-2′-pyridylimino)isoindoline (HBMePHI). Complex 1 reacts with HBMePHI, in dichloromethane, to afford equilibrium mixtures of 1, the mononuclear derivative RhCl(η4-C8H12){κ1-Npy-(HBMePHI)} (5), and the binuclear species [RhCl(η4-C8H12)]2{μ-Npy,Npy-(HBMePHI)} (6). Under the same conditions, complex 2 affords the iridium counterparts IrCl(η4-C8H12){κ1-Npy-(HBMePHI)} (7) and [IrCl(η4-C8H12)]2{μ-Npy,Npy-(HBMePHI)} (8). In contrast to chloride, one of the hydroxide groups of 3 and 4 promotes the deprotonation of HBMePHI to give [M(η4-C8H12)]2(μ-OH){μ-Npy,Niso-(BMePHI)} (M = Rh (9), Ir (10)), which are efficient precatalysts for the acceptorless and base-free dehydrogenation of secondary alcohols. In the presence of KOtBu, the [BMePHI]− ligand undergoes three different degradations: alcoholysis of an exocyclic isoindoline-N double bond, alcoholysis of a pyridyl-N bond, and opening of the five-membered ring of the isoindoline core.
publishDate 2021
dc.date.none.fl_str_mv 2021
2021
2021
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Publisher's version
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/237746
url http://hdl.handle.net/10261/237746
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2017-82935-P
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-108429RB-I00
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/RED2018-102387-T
https://doi.org/10.1021/acs.organomet.1c00068
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
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