Biscyclopentadienyl Group 6 metal complexes as metalloligands in the synthesis of heterobimetallic species. Crystal structures of new thiolato-bridged molybdenum(IV)–copper(I) complexes

Heterobimetallic complexes of the form [M(η5-C5H5)2(μ-SR)2CuLn][BF4] where M=Mo, R=Ph, L=PPh3, n=2 (1); M=W, R=Ph, L=PPh3, n=2 (2); M=Mo, R=Ph, L=PPh3, n=1 (3); M=W, R=Ph, L=PPh3, n=1 (4); M=Mo, R=Ph, L=py, n=1 (5); M=Mo, R=tBu, L=PPh3, n=1 (6); [Mo(η5-C5H5)2(μ-SPh)2CuNCMe]2[BF4]2 (7); and the trinuclear compound [{Mo(η5-C5H5)2(μ-SPh)2}2Cu][BF4] (8) have been prepared and characterised. The molecular structures of 1, 3 and 7 have been determined by single-crystal X-ray diffraction studies. The molybdenum atoms exhibit the usual bent metallocene structure with a distorted tetrahedron around each metal atom, similar to that of the free metalloligand. The coordination around the copper is tetrahedral in 1 and in the dimer 7, and trigonal distorted in 3. The MoS2Cu core is almost planar in 1, with an angle of 177.3° between the MoS2 and the CuS2 planes; this angle is 154.2° for 3, 146.2 and 149.4° for 7, and in the Cu2S2 core of the dimer the folding angle is 166.1°. The large angles at the sulphur atoms, the acute angles at the metals, the Mo–Cu distances of 4.011 Å (1), 3.664 Å (3), 3.653 and 3.649 Å (7) and the Cu–Cu distance of 3.147 Å are consistent with the absence of direct metal–metal interactions.