Substitution Reaction Studies on [Au₂Cl₂(μ-dppf)] (dppf = 1,1‘-Bis(diphenylphosphino)ferrocene). Synthesis of the First Gold(I) Complex with a μ₃-2-Pyridinethiolate Ligand

Substitution of the chlorine ligand in the complex [Au2Cl2(μ-dppf)] by other halogens or anionic ligands such as Spy- (2-pyridinethiolate) or S2CNR2- have been carried out. The complexes [Au2(Spy)2(μ-dppf)] and [Au2(S2CNR2)2(μ-dppf)] possess a nitrogen or sulfur donor atom that can coordinate to a metallic fragment; thus reactions of these complexes with [Au(OTf)(PR3)] in various molar ratios have been studied. The crystal structures of [Au2I2(μ-dppf)], [Au2Cl2(μ-dppf)], and [Au3(μ3-Spy)(μ-dppf)(PPh2Me)](OTf)2 have been established by X-ray diffraction studies. The last represents the first example where a pyridinethiolate ligand bridges three gold atoms.