Synthesis of highly stable intermediates in Michael-type additions to the double bond in (SPPh2)2C=CH2

  1. Fernández, E.J. 1
  2. Gimeno, M.C. 2
  3. Jones, P.G. 3
  4. Laguna, A. 2
  5. López-de-Luzuriaga, J.M. 1
  6. Olmos, E. 1
  1. 1 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

  2. 2 Instituto de Nanociencia y Materiales de Aragón
    info

    Instituto de Nanociencia y Materiales de Aragón

    Zaragoza, España

    ROR https://ror.org/031n2c920

  3. 3 Braunschweig University of Technology
    info

    Braunschweig University of Technology

    Brunswick, Alemania

    ROR https://ror.org/010nsgg66

Mostrar afiliaciones +
Revista:
Journal of the Chemical Society-Dalton Transactions

ISSN: 0300-9246

Año de publicación: 1997

Volumen: 19

Páginas: 3515-3518

Tipo: Artículo

SCOPUS: 2-s2.0-33749098050 WoS: WOS:A1997YB26400022 GOOGLE SCHOLAR

Otras publicaciones en: Journal of the Chemical Society-Dalton Transactions

Repositorio institucional: lock_openAcceso abierto Editor

Resumen

Treatment of vinylidenebis(diphenylphosphine) with elemental sulfur under reflux led to vinylidenebis(diphenylphosphine) disulfide, (SPPh2)2C=CH2, in good yields. Its co-ordination to a gold(III) centre activates the carbon-carbon double bond. Thus, the chelate complex [Au(C6F5)2{(SPPh2) 2C=CH2}]ClO4 reacted rapidly with carbon- or oxygen-donor nucleophiles (Nu-), such as acac- (acetylacetonate), CN-, C5H5 - or OEt-, forming methanide-type derivatives [Au(C6F5)2{(SPPh2) 2CCH2Nu}]. These products can be considered as intermediates in Michael-type additions of HNu to the C=C bond, which in this particular case display high stabilities, allowing their isolation as solids. The crystal structure of the cyclopentadienyl derivative has been established by X-ray crystallography and displays a square-planar gold(III) centre with a cis disposition of the pentafluorophenyl groups and sulfur atoms of the chelating ligand, and sp2 hybridization of the endocyclic carbon atom with partial P-C double-bond character.