Heteropolynuclear Complexes with the Ligand Ph2PCH2SPh. Theoretical Evidence for Metallophilic Au-M Attractions

  1. Fernández, E.J. 1
  2. López-de-Luzuriaga, J.M. 1
  3. Monge, M. 1
  4. Rodríguez, M.A. 1
  5. Crespo, O. 2
  6. Gimeno, M.C. 2
  7. Laguna, A. 2
  8. Jones, P.G. 3
  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

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Journal:
Chemistry - A European Journal

ISSN: 0947-6539

Year of publication: 2000

Volume: 6

Issue: 4

Pages: 636-644

Type: Article

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SCOPUS: 2-s2.0-0034681498 WoS: WOS:000085534800010 GOOGLE SCHOLAR

More publications in: Chemistry - A European Journal

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Abstract

Addition at two equivalents of diphenylthiomethylphosphine (PPh2-CH2SPh) to the starting materials [Au(tht)2]A (tht - tetrahydrothiophene), AgCF3SO3, or [Cu(CH3CN)4]CF3SO3 produces the mononuclear derivatives [M(PPh2CH2SPh)2]A (M = Au, A = CF3SO3 (1a); M = Au, A = ClO4 (1b); M = Ag, A = CF3SO3 (4); M = Cu, A = CF3SO3 (5)) which are able to form the heterodinuclear complexes [AuM (PPh2CH2SPh)2] (CF3SO3)2 (M' = Ag (2), Cu (3)) with a P-Au-P environment. If the starting gold complex is [Au(C6F5)(tht)], reaction with the phosphine produces [Au(Cf6F5)-(PPh2CH2SPh)] (6) from which, by reaction with AgCF3SO1 or [Cu(CH3CN)4]CF3SO3, the "snake"-type linear complexes [Au2M(C6F5)2-(PPh2CH 2SPh)2]CF3SO3, (M = Ag (7), Cu (8)) are obtained. If the silver starting complex is AgCF3CO2, reaction in a 1:1 ratio gives the tetranuclear complex [Au2Ag2(C6F5)2(PPh 2CH2SPh)2-(CF3CO2) 2] (9). When the molar ratio is 1:2 the trinuclear complex [AuAg2(C6F5)(CF3CO2) 2(PPh2CH2SPh)] (10) is obtained. According to ab initio calculations, the presence of only one gold atom is enough to induce metallophilic attractions in the group congeners, and this effect can be modulated depending on the gold ligand.