Synthesis of [Au<sub>2</sub>(SC<sub>6</sub>F<sub>5</sub>)<sub>2</sub>(μ-dppf)] and [Au<sub>2</sub>(μ-SC<sub>6</sub>F<sub>5</sub>)(μ-dppf)] (dppf = 1,1‘-Bis(diphenylphosphino)ferrocene). Reactivity toward Various Metallic Fragments
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The reaction of [Au2Cl2(μ-dppf)] (dppf = 1,1‘-bis(diphenylphosphino)ferrocene) with 2 equiv of pentafluorobenzenethiol in the presence of K2CO3 leads to the gold(I) thiolate derivative [Au2(SC6F5)2(μ-dppf)] (1). Complex 1 reacts with [Au(OClO3)(PR3)] in a 1:2 or 1:4 molar ratio to give [Au4(μ3-SC6F5)2(μ-dppf)(PR3)2](ClO4)2 (PR3 = PPh3 (2), PPh2Me (3)) or [Au6(μ4-SC6F5)2(μ-dppf)(PR3)4](ClO4)4 (PR3 = PPh3 (4), PPh2Me (5)), in which the thiolate ligands bridge two or three gold atoms, respectively. The treatment of 1 with [Au(C6F5)3OEt2] affords the mixed gold(I)−gold(III) species [Au4(μ3-SC6F5)2(C6F5)6(μ-dppf)] (6). Heterometallic derivatives have been obtained by reaction of 1 with copper or mercury salts and are of the type [Au2Cu(μ3-SC6F5)2Cl(μ-dppf)(PPh3)] (7), [Au6Cu2(μ3-SC6F5)6(μ-dppf)3](PF6)2 (8), or [Au2Hg(μ3-SC6F5)2X2(μ-dppf)] (X = Cl (9), I (10)). The reaction of 1 with 1 equiv of AgClO4 gives a precipitate of [Ag(SC6F5)]n and the complex [Au2(μ-SC6F5)(μ-dppf)]ClO4 (11) with the thiolate ligand bridging both gold atoms. By reaction of 11 with the gold(III) derivative [Au(C6F5)2(OEt2)2]ClO4 the complex [Au5(C6F5)2(μ3-SC6F5)2(μ-dppf)2](ClO4)3 12 can be isolated. The complexes 6 and 11 have been characterized by X-ray diffraction studies.
