Thiolate Complexes of Gold(I) Based on a Tris(phosphine) Support

Z. Naturforsch. 56 b, 1257-1263 (2001); received September 11, 2001 Gold(I) Complexes, Tri(tertiary phosphine) Complexes, Thiolate Complexes Treatment of the ligand l,3,5-tris[(diphenylphosphanyl)methyl]trimethylbenzene (P3) with (tetrahydrothiophene)gold(I) chloride results in the symmetrical trigold complex [(P3)(AuC1)3]. In the presence of sodium methoxide, [(P3)(AuC1)3] reacts with thiocresol (HSCöH4Me-4 ) and 2-mercaptoquinoline (2-HSQn) to provide the complexes [(P3)(AuSC6H4Me-4)3] and [(P3)(AuSQn)3], respectively. Reaction of [(P3)(AuCl)3] with KSCN also yields the expected product [(P3)(AuSCN)3], however, treatment with 2 1 0 molar equivalents of NaSMe re­ sults only in the unsymmetrical cationic complex [(P3)Au3(SMe)2]Cl. Reaction between [(P3)(AuOTf)3] (prepared in situ from [(P3)(AuC1)3] and AgOTf) and sodium sulfide yields the complex [(P3)Au3S]+0 S02CF3_ , the first example of a trigoldsulfonium unit coordinated to a tridentate phosphine. The tetrafluoroborate salt is obtained from [(P3)(AuCl)3] and Na2S • 9 H2O in the presence of NaBF4. The structure of [(P3)(AuSMe)2]Cl has been determined and reveals that in the solid the two methylthiolate units bridge the three gold atoms, but the structure of the cation is fiuxional in solution according to NMR data.