Substitution of the chlorine ligand in the complex [Au2Cl2(mu-dppf)] by other halogens or anionic Ligands such as Spy(-)(2-pyridinethiolate) or S2CNR2- have been carried out. The complexes [Au-2(Spy)(2)(mu-dppf)] and [Au-2(S2CNR2)(2)(mu-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(mu-dppf)], [Au2Cl2(mu-dppf)], and [Au-3(mu(3)-Spy)(mu-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.