Strong activation of the double bond in (PPh2)2C=CH2. Novel synthesis of gold(III) methanide complexes by Michael addition reactions

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

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

  2. 2 Braunschweig University of Technology
    info

    Braunschweig University of Technology

    Brunswick, Alemania

    ROR https://ror.org/010nsgg66

  3. 3 Instituto de Nanociencia y Materiales de Aragón
    info

    Instituto de Nanociencia y Materiales de Aragón

    Zaragoza, España

    ROR https://ror.org/031n2c920

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Revista:
Organometallics

ISSN: 0276-7333

Año de publicación: 1997

Volumen: 16

Número: 6

Páginas: 1130-1136

Tipo: Artículo

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SCOPUS: 2-s2.0-0011031544 WoS: WOS:A1997WN91700009 GOOGLE SCHOLAR

Otras publicaciones en: Organometallics

Repositorio institucional: lock_openAcceso abierto Editor

Resumen

Treatment of [Au(μ-Cl)(C6F5)2]2 with vinylidenebis(diphenylphosphine), (PPh2)2C=CH2, leads to the complex [Au(C6F5)2Cl{PPh2C(=CH 2)PPh2}]. The coordination of the diphosphine to a gold(III) center strongly activates the carbon-carbon double bond, and this complex, therefore, undergoes Michael-type additions with several carbon-, sulfur-, or oxygen-based nucleophiles. The complexes [Au(C6F5)2{(PPh2) 2CCH2SPh}], [Au(C6F5)2{(PPh2) 2CCH2S2-CNEt2}], and [{Au(C6F5)2{(PPh2) 2CCH2}}2O] have been structurally characterized by X-ray diffraction analysis. They show that the addition has taken place at the terminal carbon atom of the double bond, giving methanide-type complexes. Furthermore, the displacement of the ether molecules in [Au(C6F5)2(OR2)2]ClO 4 (R = Et, iPr) by the diphosphine leads, in a one pot synthesis, to the complexes [Au(C6F5)2{(PPh2) 2CHCH2OR}]ClO4 as a consequence of ether cleavage by water. © 1997 American Chemical Society.