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    • WISSENSCHAFTLICHE ARBEITEN
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    • Dpto. Química Física y Química Inorgánica
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    Por favor, use este identificador para citar o enlazar este ítem:https://uvadoc.uva.es/handle/10324/51821

    Título
    Highly efficient vinylic addition polymerization of 5-vinyl-2-norbornene using benzylic palladium complexes as precatalysts
    Autor
    Pérez Ortega, IgnacioAutoridad UVA Orcid
    Albéniz Jiménez, Ana CarmenAutoridad UVA Orcid
    Año del Documento
    2021
    Descripción
    Producción Científica
    Documento Fuente
    Polymer Chemistry, 2021, 12, 5963–5969
    Zusammenfassung
    In contrast with the parent norbornene, the vinylic addition polymerization of substituted norbornene derivatives is difficult to achieve. We have found that benzylic palladium complexes are suitable precata- lysts in the challenging vinylic addition polymerization of 5-vinyl-2-norbornene (VNB). A mixture of [Pd2(μ-Br)2(η3-C6H5CHCH2C6F5)2] (1), PCy3 and NaBArF4 leads to a very active catalyst that homopoly- merizes VNB leading to high molecular weight polymers where the exocyclic pendant double bond is preserved. Only 2 ppm of palladium are needed to obtain VA-PVNB in high yield. The order of mixing of the components of the precatalyst mixture does not affect the degree of polymerization but it influences the initiation step which occurs by insertion of VNB: (a) into a Pd–H bond generated from the neutral complex 1 or (b) into a Pd–C(benzyl) bond when the cationic [Pd(η3-C6H5CHCH2C6F5)(PCy3)(L)]BArF4 is preformed. In either case, the easy transformation from η3- to a σ-benzyl opens a coordination site on the metal that favors the initiation. The nature of the counterion is important in the propagation of the polymerization and, among several low-coordinating anions tested, BArF4− is the most efficient.
    Materias (normalizadas)
    Chemistry
    Palabras Clave
    polymerization
    vinylnorbornene
    vinylic addition polynorbornene
    palladium catalysts
    ISSN
    1759-9954
    Revisión por pares
    SI
    DOI
    10.1039/d1py01165k
    Patrocinador
    Junta de Castilla y León-FEDER (grant VA224P20)
    MICINN (PID2019-111406GB-I00 and PEJ2018-003794-A)
    Version del Editor
    https://pubs.rsc.org/en/content/articlelanding/2021/py/d1py01165k
    Idioma
    eng
    URI
    https://uvadoc.uva.es/handle/10324/51821
    Tipo de versión
    info:eu-repo/semantics/submittedVersion
    Derechos
    openAccess
    Aparece en las colecciones
    • DEP63 - Artículos de revista [322]
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    Dateien zu dieser Ressource
    Nombre:
    Polym Chem 2021 submitted Ms .pdf
    Tamaño:
    3.155Mb
    Formato:
    Adobe PDF
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