Synthesis and crystal structure of (Ph3PAu)(4)[AuMn(CO)(5)](2) and (Ph3PAu)(3)Re(CO)(4)

The reaction of [Mn(CO)(5)](-) with the cluster cation [(Ph3PAu)(8)](2+) in the yields the heterometallic cluster [(Ph3PAu)(4) [AuMn(CO)(5)](2) (1) as the main product besides small amounts of (Ph3PAu)(3)Mn(CO)(4). The former crystallizes as 1.thf in form of red blocks in the triclinic space group P (1) over bar with a = 1391.0(1), b = 1426.7(1), c = 2308.3(2) pm, alpha = 92.87(1), beta = 97.54(1), gamma = 96.43(1)degrees and Z = 2. The inner Au- 6 Skeleton of the almost centrosymmetrical cluster consists of two Au-4 tet rahedra 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 2 56.6(3) and 256.9(2) pm. By the reaction of [(Ph3PAu)(8)](2+) with [Re-2(CO )(9)](2-) the cluster (Ph3PAu)(3)Re(CO)(4) (2) is obtained in low yield bes ides the homometallic cluster [(AuPPh3)(7)](+) as the main product. 2 cryst allizes from toluene as 2.C7H8 in the form of yellow blocks with the orthor hombic 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 equator ial position. The Re-Au distances range from 271.2(1) to 273.7(1) pm, and t he Au-Au distances are 278.2(1) and 278.4(1) pm.