The reaction of [HRe 3 (CO) 12 ] 2− with an excess of Ph 3 PAuCl in CH 2 Cl 2 yields [(Ph 3 PAu) 4 Re(CO) 4 ] + as the main product, which crystallizes as [(Ph 3 PAu) 4 Re(CO) 4 ]PF 6 ·CH 2 Cl 2 (1·CH 2 Cl 2 ) after the addition of KPF 6 .The crystal structure determination reveals a trigonal bipyramidal Au 4 Re cluster with the Re atom in equatorial position.If [(Ph 3 PAu) 4 Re(CO) 4 ] + is reacted with PPh 4 Cl, a cation [Ph 3 PAu] + is eliminated as Ph 3 PAuCl, and the neutral cluster [(Ph 3 PAu) 3 Re(CO) 4 ] (2) is formed.It combines with excess [(Ph 3 PAu) 4 Re(CO) 4 ] + to afford the cluster cation, [(Ph 3 PAu) 6 AuRe 2 (CO) 8 ] + .It crystallizes from CH 2 Cl 2 as[(Ph 3 PAu) 6 AuRe 2 (CO) 8 ]PF 6 ·4CH 2 Cl 2 (3·4CH 2 Cl 2 ). In [(Ph 3 PAu) 3 Re(CO) 4 ] the metal atoms are arranged in form of a lozenge while in [(Ph 3 PAu) 6 AuRe 2 (CO) 8 ] + two Au 4 Re trigonal bipyramids are connected by a common axial Au atom.The treatment of [(Ph 3 PAu) 4 Re(CO) 4 ] + with KOH and Ph 3 PAuCl in methanol yields the cluster cation [(Ph 3 PAu) 6 Re(CO) 3 ] + , which crystallizes with PF6- from CH 2 Cl 2 as [(Ph 3 PAu) 6 Re(CO) 3 ]PF 6 ·CH 2 Cl 2 (4·CH 2 Cl 2 ). The metal atoms in this cluster form a pentagonal bipyramid with the Re atom in the axial position.