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dc.contributor.authorGallego Díaz, Ana María
dc.contributor.authorPeñas de Frutos, Marconi Nicolás 
dc.contributor.authorMarcos Ayuso, Guillermo
dc.contributor.authorMartín Álvarez, José Miguel 
dc.contributor.authorMartínez de Ilarduya Martínez de Ilarduya, Jesús María 
dc.contributor.authorEspinet Rubio, Pablo 
dc.date.accessioned2020-09-30T09:13:56Z
dc.date.available2020-09-30T09:13:56Z
dc.date.issued2020
dc.identifier.citationDalton Transactions, 2020, 49, 11336-11345es
dc.identifier.issn1477-9226es
dc.identifier.urihttp://uvadoc.uva.es/handle/10324/42666
dc.descriptionProducción Científicaes
dc.description.abstractNeutral palladium(II) complexes [Pd(Rf)X(P–L)] (Rf = 3,5-C6Cl2F3, X = Cl, I, OTf) with P–P (dppe and dppf) and P–N (PPh2(bzN)) ligands have chelated structures in the solid-state, except for P–L = dppf and X = Cl, were chelated and dimeric bridged structures are found. The species present in solution in different solvents (CDCl3, THF, NMP and HMPA) have been characterised by 19F and 31P{1H} NMR and conductivity studies. Some [Pd(Rf)X(P–L)] complexes are involved in equilibria with [Pd(Rf)(solv)(P–L)]X, depending on the solvent and X. The ΔH° and ΔS° values of these equilibria explain the variations of ionic vs. neutral complexes in the range 183–293 K. Overall the order of coordination strength of solvents and anionic ligands is: HMPA ≫ NMP > THF and I−, Cl− > TfO−. This coordination preference is determining the complexes participating in the alkynyl transmetalation from PhC[triple bond, length as m-dash]CSnBu3 to [Pd(Rf)X(P–L)] (X = OTf, I) in THF and subsequent coupling. Very different reaction rates and stability of intermediates are observed for similar complexes, revealing neglected complexities that catalytic cycles have to deal with. Rich information on the evolution of these Stille systems after transmetalation has been obtained that leads to proposal of a common behaviour for complexes with dppe and PPh2(bzN), but a different evolution for the complexes with dppf: this difference leads the latter to produce PhC[triple bond, length as m-dash]CRf and black Pd, whereas the two former yield PhC[triple bond, length as m-dash]CRf and [Pd(C[triple bond, length as m-dash]CPh)(SnBu3)(dppe)] or [Pd(C[triple bond, length as m-dash]CPh)(SnBu3){PPh2(bzN)}].es
dc.format.mimetypeapplication/pdfes
dc.language.isoenges
dc.publisherRoyal Society of Chemistryes
dc.rights.accessRightsinfo:eu-repo/semantics/openAccesses
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/4.0/*
dc.subject.classificationpalladiumes
dc.titleExperimental study of speciation and mechanistic implications when using chelating ligands in aryl-alkynyl Stille couplinges
dc.typeinfo:eu-repo/semantics/articlees
dc.rights.holder© 2020 The Royal Society of Chemistryes
dc.identifier.doi10.1039/D0DT02335Ces
dc.relation.publisherversionhttps://pubs.rsc.org/en/content/articlehtml/2020/dt/d0dt02335ces
dc.identifier.publicationfirstpage11336es
dc.identifier.publicationissue32es
dc.identifier.publicationlastpage11345es
dc.identifier.publicationtitleDalton Transactionses
dc.identifier.publicationvolume49es
dc.peerreviewedSIes
dc.description.projectMinisterio de Economía, Industria y Competitividad (projects CTQ2016-80913-P and CTQ2017-89217-P)es
dc.description.projectJunta de Castilla y León (project VA062G18, UIC 176)es
dc.identifier.essn1477-9234es
dc.rightsAttribution-NonCommercial-NoDerivatives 4.0 Internacional*
dc.type.hasVersioninfo:eu-repo/semantics/submittedVersiones


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