Isolation of bis- and mono-cyclometallated Ru−IMes complexes upon reaction of [Ru(PPh3)3HCl], IMes and ZnMe2

Addition of an excess of ZnMe2 to a mixture of [Ru(PPh3)3HCl] and IMes (IMes=1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene) yields the bis-cyclometallated complex, [Ru(IMes)“(PPh3)2] 2, together with the mono-cyclometallated, Ru−Zn heterobimetallic complex [Ru(IMes)′(PPh3)2(ZnMe)] 3. Treatment...

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Autores: Pécharman, Anne-Frédérique M., Roberts, Erika M., Miloserdov, Fedor M., Varela-Izquierdo, Víctor, Mahon, Mary F., Whittlesey, Michael K.
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2023
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/334717
Acceso en línea:http://hdl.handle.net/10261/334717
Access Level:acceso abierto
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spelling Isolation of bis- and mono-cyclometallated Ru−IMes complexes upon reaction of [Ru(PPh3)3HCl], IMes and ZnMe2Pécharman, Anne-Frédérique M.Roberts, Erika M.Miloserdov, Fedor M.Varela-Izquierdo, VíctorMahon, Mary F.Whittlesey, Michael K.Addition of an excess of ZnMe2 to a mixture of [Ru(PPh3)3HCl] and IMes (IMes=1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene) yields the bis-cyclometallated complex, [Ru(IMes)“(PPh3)2] 2, together with the mono-cyclometallated, Ru−Zn heterobimetallic complex [Ru(IMes)′(PPh3)2(ZnMe)] 3. Treatment of 2 with H2, PhSiH3 or pinacolborane yields the previously reported complex, [Ru(IMes)′(PPh3)2H] 1, the synthesis of which has been reinvestigated. Further studies of small molecule reactivity show that 1 adds H2 to give [Ru(IMes)(PPh3)2H4] 4, whilst 2 reacts with catecholborane to give [Ru(IMes-Bcat)′(PPh3)2H] 5, in which (IMes-Bcat)′ signifies a borylated NHC ligand that is singly-metallated onto Ru. Treatment of 2 with CO gives the 18-electron dicarbonyl product [Ru(IMes)”(PPh3)(CO)2] 6. Compounds 1–3, 5 and 6 have been structurally characterised.This work was supported by the EPSRC (grant EP/T019743/1 for AFP) and the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No 792674 (FMM). VVI thanks MINECO/FEDER (CTQ2017-83421-P) and Gobierno de Aragón (GA/FEDER, Inorganic Molecular Architecture Group E08_17R) for financial support and MINECO/FEDER for a FPI fellowship.Peer reviewedWiley-VCHEngineering and Physical Sciences Research Council (UK)Agencia Estatal de Investigación (España)Ministerio de Ciencia, Innovación y Universidades (España)Gobierno de AragónEuropean CommissionConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202320232023info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10261/334717reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/EC/H2020/792674info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2017-83421-PThe underlying dataset has been published as supplementary material of the article in the publisher platform at DOI 10.1002/ejic.202300037https://doi.org/10.1002/ejic.202300037Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3347172026-05-22T06:33:51Z
dc.title.none.fl_str_mv Isolation of bis- and mono-cyclometallated Ru−IMes complexes upon reaction of [Ru(PPh3)3HCl], IMes and ZnMe2
title Isolation of bis- and mono-cyclometallated Ru−IMes complexes upon reaction of [Ru(PPh3)3HCl], IMes and ZnMe2
spellingShingle Isolation of bis- and mono-cyclometallated Ru−IMes complexes upon reaction of [Ru(PPh3)3HCl], IMes and ZnMe2
Pécharman, Anne-Frédérique M.
title_short Isolation of bis- and mono-cyclometallated Ru−IMes complexes upon reaction of [Ru(PPh3)3HCl], IMes and ZnMe2
title_full Isolation of bis- and mono-cyclometallated Ru−IMes complexes upon reaction of [Ru(PPh3)3HCl], IMes and ZnMe2
title_fullStr Isolation of bis- and mono-cyclometallated Ru−IMes complexes upon reaction of [Ru(PPh3)3HCl], IMes and ZnMe2
title_full_unstemmed Isolation of bis- and mono-cyclometallated Ru−IMes complexes upon reaction of [Ru(PPh3)3HCl], IMes and ZnMe2
title_sort Isolation of bis- and mono-cyclometallated Ru−IMes complexes upon reaction of [Ru(PPh3)3HCl], IMes and ZnMe2
dc.creator.none.fl_str_mv Pécharman, Anne-Frédérique M.
Roberts, Erika M.
Miloserdov, Fedor M.
Varela-Izquierdo, Víctor
Mahon, Mary F.
Whittlesey, Michael K.
author Pécharman, Anne-Frédérique M.
author_facet Pécharman, Anne-Frédérique M.
Roberts, Erika M.
Miloserdov, Fedor M.
Varela-Izquierdo, Víctor
Mahon, Mary F.
Whittlesey, Michael K.
author_role author
author2 Roberts, Erika M.
Miloserdov, Fedor M.
Varela-Izquierdo, Víctor
Mahon, Mary F.
Whittlesey, Michael K.
author2_role author
author
author
author
author
dc.contributor.none.fl_str_mv Engineering and Physical Sciences Research Council (UK)
Agencia Estatal de Investigación (España)
Ministerio de Ciencia, Innovación y Universidades (España)
Gobierno de Aragón
European Commission
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description Addition of an excess of ZnMe2 to a mixture of [Ru(PPh3)3HCl] and IMes (IMes=1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene) yields the bis-cyclometallated complex, [Ru(IMes)“(PPh3)2] 2, together with the mono-cyclometallated, Ru−Zn heterobimetallic complex [Ru(IMes)′(PPh3)2(ZnMe)] 3. Treatment of 2 with H2, PhSiH3 or pinacolborane yields the previously reported complex, [Ru(IMes)′(PPh3)2H] 1, the synthesis of which has been reinvestigated. Further studies of small molecule reactivity show that 1 adds H2 to give [Ru(IMes)(PPh3)2H4] 4, whilst 2 reacts with catecholborane to give [Ru(IMes-Bcat)′(PPh3)2H] 5, in which (IMes-Bcat)′ signifies a borylated NHC ligand that is singly-metallated onto Ru. Treatment of 2 with CO gives the 18-electron dicarbonyl product [Ru(IMes)”(PPh3)(CO)2] 6. Compounds 1–3, 5 and 6 have been structurally characterised.
publishDate 2023
dc.date.none.fl_str_mv 2023
2023
2023
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/10261/334717
url http://hdl.handle.net/10261/334717
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#
info:eu-repo/grantAgreement/EC/H2020/792674
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2017-83421-P
The underlying dataset has been published as supplementary material of the article in the publisher platform at DOI 10.1002/ejic.202300037
https://doi.org/10.1002/ejic.202300037
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
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
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