Synthesis and Characterization of Gold(I) Complexes with the Ligand 1,2-Dithiolate-o-carborane. Crystal Structures of [Au2(μ-S2C2B10H10)(PPh3)2], [Au2(μ-S2C2B10H10)(μ-{(PPh2)2(CHCH)}], and [Au2(μ-S2C2B10H10)(μ-{(PPh2)2(C6H4)}]

Treatment of 1,2-dimercapto- o -carborane with 2 equiv of [AuClL] in the presence of Na 2 CO 3 gave the dinuclear complexes [Au 2 (μ-S 2 C 2 B 10 H 10 )L 2 ] [L = PPh 3 ( 1 ), PPh 2 Me ( 2 ), PPh 2 (C 6 H 4 Me-4) ( 3 ), SPPh 3 ( 4 )] where the dithiolate ligand bridges both gold atoms. Further reaction of 1 with [Au(OTf)(PPh 3 )] (OTf = trifluoromethanesulfonate) leads to the trinuclear species [Au 3 (S 2 C 2 B 10 H 10 )(PPh 3 ) 3 ](OTf) ( 5 ). The anionic derivative (PPh 3 Me) 2 [Au 2 (C 6 F 5 ) 2 (μ-S 2 C 2 B 10 H 10 )] ( 6 ) was prepared by reaction of 1,2-(SH) 2 C 2 B 10 H 10 with (PPh 3 Me)[AuBr(C 6 F 5 )]. Dinuclear complexes with two bridging ligands were synthesized: the neutral heterobridged species [Au 2 (μ-S 2 C 2 B 10 H 10 )(μ-P−P)] [P−P = dppm ( 7 ), dppey ( 8 ), dppp ( 9 ), dppph ( 10 ), dppe ( 11 )] obtained from 1,2-(SH) 2 C 2 B 10 H 10 and [Au 2 Cl 2 (μ-P−P)] and the homobridged anionic derivative NBu 4 [Au 2 (μ-S 2 C 2 B 10 H 10 ) 2 ] ( 12 ) prepared by treatment of the 1,2-dimercapto- o -carborane with [AuCl(tht)] (tht = tetrahydrothiophene) (molar ratio 1:1) and NBu 4 Br. The crystal structures of complexes 1, 8, and 10 were determined by X-ray diffraction studies.