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The photolysis of Cr(CO) 6  and Ph 3 PAuN 3  (1:2) in thf yields the unstable cluster cation [(Ph 3 PAu) 5 Cr(CO) 4 ] +  that slowly decomposes to form the new homometallic gold cluster [Au(AuNCO)(AuPPh 3 ) 8 ]Cl. The cluster compound crystallizes in form of red needles in the tetragonal space group I4 with a = 2214.1(3), c = 1408.9(2) pm, and Z = 2. The inner skeleton of the cluster with the symmetry C 4  consists of a centered square antiprism of nine Au atoms with the square faces of the antiprism being bridged by the AuNCO group, and a Cl -  anion, respectively. The shortest Au-Au distances exist between the central and the 8+1 peripheral Au atoms ranging between 263.5( 1) and 270.6(3) pm, the four Au-Cl distances are 280(1) pm.

Synthese und Kristallstruktur von [Au(AuNCO)(AuPPh 3 ) 8 ]Cl / Synthesis and Crystal Structure of [Au(AuNCO)(AuPPh 3 ) 8 ]Cl