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    Por favor, use este identificador para citar o enlazar este ítem:http://uvadoc.uva.es/handle/10324/28846

    Título
    Polymer [Pd(CH2SO2C6H4Me)2]n, a precursor to remarkably stable Pd organometallics
    Autor
    Pérez Briso, Celeste
    Gallego Diaz, Ana MaríaAutoridad 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
    2017
    Editorial
    Royal Society of Chemistry
    Descripción
    Producción Científica
    Documento Fuente
    Dalton Transactions, 2017, 46, 25, p. 8083-8090
    Abstract
    A polymer [Pd(CH2SO2C6H4Me)2]n is obtained by thermolysis of cis-[Pd(CH2SO2C6H4Me)2(NCMe)2] to release the MeCN ligands. The corresponding coordination sites are then occupied by weak Pd–O bonds, easier to break than the previous Pd–N bonds. This allows us to produce from the polymer cis complexes containing ligands weaker than NCMe, such as acetone or water. The complexes cis-[Pd(CH2SO2C6H4Me)2{OC(CD3)2}2], cis-[Pd(CH2SO2C6H4Me)2(OH2)2], and cis-[Pd(CH2SO2C6H4Me)2(OH2){OC(CD3)2}], and cyclic dimers [Pd(CH2SO2C6H4Me)2(OH2)]2 with bridging methylsulphone groups are formed. The Pd : PPh3 : OH2 1 : 1 : 1 reaction of the polymer produces cis-[Pd(CH2SO2C6H4Me)2(OH2)(PPh3)], which isomerizes to trans-[Pd(CH2SO2C6H4Me)2(OH2)(PPh3)], with water O-coordinated to Pd and making hydrogen bonds to the two SO2 groups as seen in its X-ray structure. A similar role is played by RNH2 groups in the structures of trans-[Pd(CH2SO2C6H4Me)2(NH3)(PPh3)] and the dimer μ-(N2H4)(trans-[Pd(CH2SO2C6H4Me)2(PPh3)])2. In addition to these interesting intramolecular hydrogen bonding properties provided by the SO2 groups, the structural and 1H NMR data available suggest that the CH2SO2C6H4Me group is an interesting kind of strong alkyl σ donor, with high trans influence, and forms very stable Pd complexes extraordinarily resistant to reductive elimination and to hydrolysis by water at room temperature.
    Palabras Clave
    Polímeros
    Compuestos organometálicos
    ISSN
    1477-9226
    Revisión por pares
    SI
    DOI
    10.1039/c7dt00904f
    Patrocinador
    Ministerio de Economía, Industria y Competitividad (Projects CTQ2014-52796-P and CTQ2016-80913-P)
    Junta de Castilla y León (programa de apoyo a proyectos de investigación – Ref. VA256U13; UIC 176)
    Version del Editor
    http://pubs.rsc.org/en/content/articlelanding/2017/dt/c7dt00904f
    Idioma
    eng
    URI
    http://uvadoc.uva.es/handle/10324/28846
    Derechos
    openAccess
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    • DEP63 - Artículos de revista [334]
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    Universidad de Valladolid

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