Heteropolynuclear Complexes with the Ligand Ph2PCH2SPh. Theoretical Evidence for Metallophilic Au-M Attractions
- Fernández, E.J. 1
- López-de-Luzuriaga, J.M. 1
- Monge, M. 1
- Rodríguez, M.A. 1
- Crespo, O. 2
- Gimeno, M.C. 2
- Laguna, A. 2
- Jones, P.G. 3
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1
Universidad de La Rioja
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2
Instituto de Nanociencia y Materiales de Aragón
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3
Braunschweig University of Technology
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ISSN: 0947-6539
Any de publicació: 2000
Volum: 6
Número: 4
Pàgines: 636-644
Tipus: Article
Altres publicacions en: Chemistry - A European Journal
Resum
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.