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    Por favor, use este identificador para citar o enlazar este ítem:http://uvadoc.uva.es/handle/10324/42666

    Título
    Experimental study of speciation and mechanistic implications when using chelating ligands in aryl-alkynyl Stille coupling
    Autor
    Gallego Diaz, Ana MaríaAutoridad UVA Orcid
    Peñas de Frutos, Marconi NicolásAutoridad UVA Orcid
    Marcos Ayuso, GuillermoAutoridad UVA Orcid
    Martín Álvarez, José MiguelAutoridad UVA Orcid
    Martínez de Ilarduya Martínez de Ilarduya, Jesús MaríaAutoridad UVA Orcid
    Espinet Rubio, PabloAutoridad UVA Orcid
    Año del Documento
    2020
    Editorial
    Royal Society of Chemistry
    Descripción
    Producción Científica
    Documento Fuente
    Dalton Transactions, 2020, 49, 11336-11345
    Abstract
    Neutral 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)}].
    Palabras Clave
    palladium
    ISSN
    1477-9226
    Revisión por pares
    SI
    DOI
    10.1039/D0DT02335C
    Patrocinador
    Ministerio de Economía, Industria y Competitividad (projects CTQ2016-80913-P and CTQ2017-89217-P)
    Junta de Castilla y León (project VA062G18, UIC 176)
    Version del Editor
    https://pubs.rsc.org/en/content/articlehtml/2020/dt/d0dt02335c
    Propietario de los Derechos
    © 2020 The Royal Society of Chemistry
    Idioma
    eng
    URI
    http://uvadoc.uva.es/handle/10324/42666
    Tipo de versión
    info:eu-repo/semantics/submittedVersion
    Derechos
    openAccess
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    • CINQUIMA - Artículos de revista [162]
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    Chelates-Alkyny-revised Clean[19474]-XX.pdf
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    Attribution-NonCommercial-NoDerivatives 4.0 InternacionalExcept where otherwise noted, this item's license is described as Attribution-NonCommercial-NoDerivatives 4.0 Internacional

    Universidad de Valladolid

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