Synthesis of [Au-2(SC6F5)(2)(mu-dppf)] and [Au-2(mu-SC6F5)(mu-dppf)] (dppf=1,1 '-bis(diphenylphosphino)ferrocene). Reactivity toward various metallicfragments

The reaction of [Au2Cl2(mu-dppf)] (dppf = 1,1'-bis(diphenylphosphino)ferroc ene) with 2 equiv of pentafluorobenzenethiol in the presence of K2CO3 leads to the gold(I) thiolate derivative [Au-2(SC6F5)(2)(mu-dppf)] (1). Complex 1 reacts with [Au(OClO3)(PR3)] in a 1:2 or 1:4 molar ratio to give [Au-4(mu (3)-SC6F5)(2)(mu-dppf)(PR3)(2)](ClO4)(2) (PR3 = PPh3 (2), PPh2Me (3)) or [A u-6(mu(4)-SC6F5)(2)-(mu-dppf)(PR3)(4)](ClO4)(4) (PR3 = PPh3 (4), PPh2Me (5) ), in which the thiolate ligands bridge two or three gold atoms, respective ly. The treatment of 1 with [Au(C6F5)(3)OEt2] affords the mixed gold(I)-gol d(III) species [Au-4(mu(3)-SC6F5)(2)(C6F5)(6)(mu-dppf)] (6). Heterometallic derivatives have been obtained by reaction of 1 with copper or mercury sal ts and are of the type [Au-2-Cu(mu(3)-SC6F5)(2)Cl(mu-dppf)(PPh3)] (7), [Au6 Cu2(mu(3)-SC6F5)(6)(mu-dppf)(3)](PF6)(2) (8), or [Au2Hg(mu(3)-SC6F5)(2)X-2( mu-dppf)] (X = Cl (9), I (10)). The reaction of 1 with 1 equiv of AgClO4 gi ves a precipitate of [Ag(SC6F5)](n) and the complex [Au-2(mu-SC6F5)(mu-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 comple x [Au-5(C6F5)(2)(mu(3)-SC6F5)(2)(mu-dppf)(2)](ClO4)(3) 12 can be isolated. The complexes 6 and 11 have been characterized by X-ray diffraction studies .