The new 2-phenylthiocarbamoyl-1,3-dimesitylimidazolium inner salt (IMes·CSNPh) reacts with [AuCl(L)] in the presence of NH(4)PF(6) to yield [(L)Au(SCNPh·IMes)](+) (L = PMe(3), PPh(3), PCy(3), CNBu(t)). The carbene-containing precursor [(IDip)AuCl] reacts with IMes·CSNPh under the same conditions to afford the complex [(IDip)Au(SCNPh·IMes)](+) (IDip = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene). Treatment of the diphosphine complex [(dppm)(AuCl)(2)] with one equivalent of IMes·CSNPh yields the digold metallacycle, [(dppm)Au(2)(SCNPh·IMes)](2+), while reaction of [L(2)(AuCl)(2)] with two equivalents of IMes·CSNPh results in [(L(2)){Au(SCNPh·IMes)}(2)](2+) (L(2) = dppb, dppf, or dppa; dppb = 1,4-bis(diphenylphosphino)butane, dppf = 1,1'-bis(diphenylphosphino)ferrocene, dppa = 1,4-bis(diphenylphosphino)acetylene). The homoleptic complex [Au(SCNPh·IMes)(2)](+) is formed on reaction of [AuCl(tht)] (tht = tetrahydrothiophene) with two equivalents of the imidazolium-2-phenylthiocarbamoyl ligand. This product reacts with AgOTf to yield the mixed metal compound [AuAg(SCNPh·IMes)(2)](2+). Over time, the unusual trimetallic complex [Au(AgOTf)(2)(SCNPh·IMes)(2)](+) is formed. The sulfur-oxygen mixed-donor ligands IMes·COS and SIMes·COS (SIMes = 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene) were used to prepare [(L)Au(SOC·IMes)](+) and [(L)Au(SOC·SIMes)](+) from [(L)AuCl] (L = PPh(3), CN(t)Bu). The bimetallic examples [(dppf){Au(SOC·IMes)}(2)](2+) and [(dppf){Au(SOC·SIMes)}(2)](2+) were synthesized from the reaction of [(dppf)(AuCl)(2)] with the appropriate ligand. Reaction of [(tht)AuCl] with one equivalent of IMes·COS or SIMes·COS yields [Au(SOC·IMes)(2)](+) and [Au(SOC·SIMes)(2)](+), respectively. The compounds [(Ph(3)P)Au(SCNPh·IMes)]PF(6), [(Cy(3)P)Au(SCNPh·IMes)]PF(6) and [Au(AgOTf)(2)(SCNPh·IMes)(2)]OTf were characterized crystallographically.
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