Aurophilicity at sulfur centers. Synthesis and reactivity of the complex (S(Au2dppf)); formation of polynuclear sulfur-centered complexes. Crystal structures of (S(Au2dppf)).2CHCl3, ((mu-Au2dppf)(S(Au2dppf))2)(OTf)2.8CHCl3, and (S(AuPPh2Me)2(Au2dppf))(ClO4)2.3CH2Cl2

The sulphur atom in the complex (S(Au2dppf)) can give trinuclear neutral (S(Au(C6F5))(Au2dppf)) or cationic derivatives (S(AuL)-(Au2dppf))ClO4 by coordinating neutral or cationic gold(I) fragments. The dppf in the compound is 1,1'-bis(diphenylphosphino)ferrocene and L is CH2PPh3, PPh3 or PPh2Me. Tri- and tetranuclear complex formation also occurs and they show short gold(I)-gold(I) interactions. The (S(AuL)4) monomer structure may be affected by the ligand attached to Au. Crystallographic data of the complexes obtained from nuclear magnetic resonance spectra analysis are given.