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289ChemInform Abstract The reactivity of several mixed-metal gold clusters toward PPh3 (II) is investigated. The reactions of PPh3 with the Au5Re cluster (I), the RuAu2 cluster (V), the IrAu clusters (IX) and (X) lead to elimination of (Au(PPh3)2)+ (IV) and to formation of the products (III), (VI), (VII), and (XI), respectively. The new mixed-metal gold compounds (XIV) and (XVII) are prepared according to the scheme; these do not readily react with PPh3. All these clusters are characterized by 1H and 31P NMR spectroscopy. The structure of (III) (space group P2/c, Z=4) is confirmed by single-crystal X-ray analysis at -95 rc C.