Synthesis of [Au2(SC6F5)2(μ-dppf)] and [Au2(μ-SC6F5)(μ-dppf)] (dppf = 1,1‘-Bis(diphenylphosphino)ferrocene). Reactivity toward Various Metallic Fragments

The reaction of [Au 2 Cl 2 (μ-dppf)] (dppf = 1,1‘-bis(diphenylphosphino)ferrocene) with 2 equiv of pentafluorobenzenethiol in the presence of K 2 CO 3 leads to the gold(I) thiolate derivative [Au 2 (SC 6 F 5 ) 2 (μ-dppf)] ( 1 ). Complex 1 reacts with [Au(OClO 3 )(PR 3 )] in a 1:2 or 1:4 molar ratio to give [Au 4 (μ 3 -SC 6 F 5 ) 2 (μ-dppf)(PR 3 ) 2 ](ClO 4 ) 2 (PR 3 = PPh 3 ( 2 ), PPh 2 Me ( 3 )) or [Au 6 (μ 4 -SC 6 F 5 ) 2 (μ-dppf)(PR 3 ) 4 ](ClO 4 ) 4 (PR 3 = PPh 3 ( 4 ), PPh 2 Me ( 5 )), in which the thiolate ligands bridge two or three gold atoms, respectively. The treatment of 1 with [Au(C 6 F 5 ) 3 OEt 2 ] affords the mixed gold(I)−gold(III) species [Au 4 (μ 3 -SC 6 F 5 ) 2 (C 6 F 5 ) 6 (μ-dppf)] ( 6 ). Heterometallic derivatives have been obtained by reaction of 1 with copper or mercury salts and are of the type [Au 2 Cu(μ 3 -SC 6 F 5 ) 2 Cl(μ-dppf)(PPh 3 )] ( 7 ), [Au 6 Cu 2 (μ 3 -SC 6 F 5 ) 6 (μ-dppf) 3 ](PF 6 ) 2 ( 8 ), or [Au 2 Hg(μ 3 -SC 6 F 5 ) 2 X 2 (μ-dppf)] (X = Cl ( 9 ), I ( 10 )). The reaction of 1 with 1 equiv of AgClO 4 gives a precipitate of [Ag(SC 6 F 5 )] n and the complex [Au 2 (μ-SC 6 F 5 )(μ-dppf)]ClO 4 ( 11) with the thiolate ligand bridging both gold atoms. By reaction of 11 with the gold(III) derivative [Au(C 6 F 5 ) 2 (OEt 2 ) 2 ]ClO 4 the complex [Au 5 (C 6 F 5 ) 2 (μ 3 -SC 6 F 5 ) 2 (μ-dppf) 2 ](ClO 4 ) 3 12 can be isolated. The complexes 6 and 11 have been characterized by X-ray diffraction studies.