Synthesis and Characterization of Gold(I) Complexes with the Ligand 1,2-Dithiolate-<i>o</i>-carborane. Crystal Structures of [Au<sub>2</sub>(μ-S<sub>2</sub>C<sub>2</sub>B<sub>10</sub>H<sub>10</sub>)(PPh<sub>3</sub>)<sub>2</sub>], [Au<sub>2</sub>(μ-S<sub>2</sub>C<sub>2</sub>B<sub>10</sub>H<sub>10</sub>)(μ-{(PPh<sub>2</sub>)<sub>2</sub>(CHCH)}], and [Au<sub>2</sub>(μ-S<sub>2</sub>C<sub>2</sub>B<sub>10</sub>H<sub>10</sub>)(μ-{(PPh<sub>2</sub>)<sub>2</sub>(C<sub>6</sub>H<sub>4</sub>)}]
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Treatment of 1,2-dimercapto-o-carborane with 2 equiv of [AuClL] in the presence of Na2CO3 gave the dinuclear complexes [Au2(μ-S2C2B10H10)L2] [L = PPh3 (1), PPh2Me (2), PPh2(C6H4Me-4) (3), SPPh3 (4)] where the dithiolate ligand bridges both gold atoms. Further reaction of 1 with [Au(OTf)(PPh3)] (OTf = trifluoromethanesulfonate) leads to the trinuclear species [Au3(S2C2B10H10)(PPh3)3](OTf) (5). The anionic derivative (PPh3Me)2[Au2(C6F5)2(μ-S2C2B10H10)] (6) was prepared by reaction of 1,2-(SH)2C2B10H10 with (PPh3Me)[AuBr(C6F5)]. Dinuclear complexes with two bridging ligands were synthesized: the neutral heterobridged species [Au2(μ-S2C2B10H10)(μ-P−P)] [P−P = dppm (7), dppey (8), dppp (9), dppph (10), dppe (11)] obtained from 1,2-(SH)2C2B10H10 and [Au2Cl2(μ-P−P)] and the homobridged anionic derivative NBu4[Au2(μ-S2C2B10H10)2] (12) prepared by treatment of the 1,2-dimercapto-o-carborane with [AuCl(tht)] (tht = tetrahydrothiophene) (molar ratio 1:1) and NBu4Br. The crystal structures of complexes 1, 8, and 10 were determined by X-ray diffraction studies.
