Pseudo-tetrahedral rhodium and iridium complexes: Catalytic synthesis of E-enynes

Dedicated in Memoriam to Professor Dr. Pascual Royo.

Detalles Bibliográficos
Autores: Geer, Ana M., Julián, Alejandro, López, José A., Ciriano, Miguel A., Tejel, Cristina
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2018
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/174218
Acceso en línea:http://hdl.handle.net/10261/174218
Access Level:acceso abierto
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spelling Pseudo-tetrahedral rhodium and iridium complexes: Catalytic synthesis of E-enynesGeer, Ana M.Julián, AlejandroLópez, José A.Ciriano, Miguel A.Tejel, CristinaDedicated in Memoriam to Professor Dr. Pascual Royo.The reactions of the rhodium(I) and iridium(I) complexes [M(PhBP3)(C2H4)(NCMe)] (PhBP3=PhB(CH2PPh2)3−) with alkynes have resulted in the synthesis of a new family of pseudo‐tetrahedral complexes, [M(PhBP3)(RC≡CR′)] (M=Rh, Ir), which contain the alkyne as a four‐electron donor. The reactions of these unusual compounds with two‐electron donors (L=PMe3, CNtBu) produced a change in the “donicity” of the alkyne from a 4e− to a 2e− donor to give five‐coordinate complexes. These were the final products with the iridium complexes, whereas further reactions took place with the rhodium complexes. In particular, C(sp)−H bond activation of the alkyne occurred leading to hydrido alkynyl complexes. This process is essential for the further reactivity of the alkynes, and if the alkyne itself was used as reagent, E‐enyne complexes were obtained. As a consequence of this chemistry, we show that the complex [Rh(PhBP3)(C2H4)(NCMe)] is a very efficient pre‐catalyst for the regioselective di‐ and trimerization of terminal alkynes to E‐enynes and benzene derivatives, respectively. Interestingly, acetonitrile significantly enhanced the catalytic activity by facilitating the C(sp)−H bond activation step. A hydrometalation mechanism to account for these experimental observations is proposed.The generous financial support from the MINECO/FEDER (Projects CTQ2014‐53033‐P and CTQ2017‐83421‐P, C.T.) and the Gobierno de Aragón/FEDER (GA/FEDER, Inorganic Molecular Architecture Group E08_17R; C.T.) is gratefully acknowledged.Peer ReviewedWiley-VCHMinisterio de Economía, Industria y Competitividad (España)Agencia Estatal de Investigación (España)Gobierno de AragónEuropean CommissionMinisterio de Economía y Competitividad (España)Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]2019201920182019info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionhttp://hdl.handle.net/10261/174218reponame: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#CTQ2017‐83421‐P/AEI/10.13039/501100011033info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/CTQ2017‐83421‐Pinfo:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2014‐53033‐Phttps://doi.org/10.1002/chem.201803878Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/1742182026-05-22T06:33:51Z
dc.title.none.fl_str_mv Pseudo-tetrahedral rhodium and iridium complexes: Catalytic synthesis of E-enynes
title Pseudo-tetrahedral rhodium and iridium complexes: Catalytic synthesis of E-enynes
spellingShingle Pseudo-tetrahedral rhodium and iridium complexes: Catalytic synthesis of E-enynes
Geer, Ana M.
title_short Pseudo-tetrahedral rhodium and iridium complexes: Catalytic synthesis of E-enynes
title_full Pseudo-tetrahedral rhodium and iridium complexes: Catalytic synthesis of E-enynes
title_fullStr Pseudo-tetrahedral rhodium and iridium complexes: Catalytic synthesis of E-enynes
title_full_unstemmed Pseudo-tetrahedral rhodium and iridium complexes: Catalytic synthesis of E-enynes
title_sort Pseudo-tetrahedral rhodium and iridium complexes: Catalytic synthesis of E-enynes
dc.creator.none.fl_str_mv Geer, Ana M.
Julián, Alejandro
López, José A.
Ciriano, Miguel A.
Tejel, Cristina
author Geer, Ana M.
author_facet Geer, Ana M.
Julián, Alejandro
López, José A.
Ciriano, Miguel A.
Tejel, Cristina
author_role author
author2 Julián, Alejandro
López, José A.
Ciriano, Miguel A.
Tejel, Cristina
author2_role author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Economía, Industria y Competitividad (España)
Agencia Estatal de Investigación (España)
Gobierno de Aragón
European Commission
Ministerio de Economía y Competitividad (España)
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description Dedicated in Memoriam to Professor Dr. Pascual Royo.
publishDate 2018
dc.date.none.fl_str_mv 2018
2019
2019
2019
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Postprint
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/174218
url http://hdl.handle.net/10261/174218
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#
CTQ2017‐83421‐P/AEI/10.13039/501100011033
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/CTQ2017‐83421‐P
info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2014‐53033‐P
https://doi.org/10.1002/chem.201803878
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Wiley-VCH
publisher.none.fl_str_mv Wiley-VCH
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
repository.name.fl_str_mv
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