Pt(CN)(AuCN)(AuPPh3)8+ (1) can be prepared from Pt(AuPPh3)82+ (2) by an oxidative addition reaction with Au(CN)2-. The CO in Pt(CO)(Au- PPh3)82+ cannot be replaced with CN-, but in a slow process two PPh3 are replaced, forming Pt(CO)(Au- CN)2(AuPPh3)6 (3). The compounds are characterized by 31P, 13C and 195Pt NMR, FAB-MS and IR measurements. The structure of Pt(CN)(AuCN)- (AuPPh3)8(NO3) is determined by X-ray diffraction (monoclinic, space group P21/n, a = 17.269(20), b = 29.638(17), c = 27.88(3) Å, β = 93.95(14)°, V = 14233 Å3, Z = 4, the residuals are R = 0.063 and Rw = 0.090 for 5965 observed reflections and 467 variables Cu Kα radiation). In the metal cluster the central Pt atom is surrounded by eight Au atoms and one CN ligand in a spheroidal structure similar to that of Pt(CO)(AgNO3)(AuPPh3)82+. © 1990.