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The reaction of [Mn(CO) 5 ] -  with the cluster cation [(Ph 3 PAu) 8 ] 2+  in thf yields the heterometallic cluster [(Ph 3 PAu) 4  [AuMn(CO) 5 ] 2  (1) as the main product besides small amounts of (Ph 3 PAu) 3 Mn(CO) 4 . The former crystallizes as 1-thf in form of red blocks in the triclinic space group P1 with a = 1391,0( 1), b = 1426.7( 1), c = 2308.3(2) pm, α = 92.87(1), β = 97.54( 1), γ = 96.43(1)° and Z = 2. The inner Au 6  skeleton of the almost centrosymmetrical cluster consists of two Au 4  tetrahedra sharing one edge. Two gold atoms bind a Mn(CO) 5  fragment, whereas to the other four gold atoms phosphine ligands are coordinated. The Au-Au distances range from 263.2(1) to 281.9(1) pm, and the Au-Mn distances are 256.6(3) and 256.9(2) pm. By the reaction of [(Ph 3 PAu) 8 ] 2+  with [Re 2 (CO) 9 ] 2-  the cluster (Ph 3 PAu) 3 Re(CO) 4  (2) is obtained in low yield besides the homometallic cluster [(AuPPh 3 ) 7 ] +  as the main product. 2 crystallizes from toluene as 2 C 7 H 8  in the form of yellow blocks with the orthorhombic space group Pna2 1 , and a = 1758.7(3), b = 1648.7(5), c = 2049.3(5) pm. The four metal atoms form a planar lozenge with the Re atom in equatorial position. The Re-Au distances range from 271.2(1) to 273.7(1) pm, and the Au-Au distances are 278.2(1) and 278.4(1) pm

zeitschrift für naturforschung b

Synthese und Kristallstruktur von (Ph 3 PAu) 4 [AuMn(CO) 5 ] 2  und (Ph 3 PAu) 3 Re(CO) 4 / Synthesis and Crystal Structure of (Ph 3 PAu) 4  [AuMn(CO) 5 ] 2  and (Ph 3 PAu) 3 Re(CO) 4