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

摘要

Heterobimetallic complexes of the form [M(#eta#~5-C_5H_5)_2(#mu#-SR)_2CuL_n][BF_4] where M = Mo, R = Ph, L = PPh_3, n = 2 (1); M = W, R = Ph, L = PPh_3, n = 2 (2); M = Mo, R = Ph, L = PPh_3, n = 1 (3); M = W, R = Ph, L = PPh_3, n = 1 (4); M = Mo, R = Ph, L = py, n = 1 (5); M = Mo, R = ~tBu, L = PPh_3, n = 1 (6); [Mo(#eta#~5-C_5H_5)_2(#mu#-SPh)_2CuNCMe]_2[BF_4]_2 (7); and the trinuclear compound [{[Mo(#eta#~5-C_5H_5)_2(#mu#-SPh)_2]_2Cu] [BF_4] (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 MoS_2Cu core is almost planar in 1, with an angle of 177.3 deg between the MoS_2 and the CuS_2 planes; this angle is 154.2 deg for 3, 146.2 and 149.4 deg for 7, and in the Cu_2S_2 core of the dimer the folding angle is 166.1 deg . The large angles at the sulphur atoms, the acute angles at the metals, the Mo-Cu distances of 4.011 A (1), 3.664 A (3), 3.653 and 3.649 A (7) and the Cu-Cu distance of 3.147 A are consistent with the absence of direct metal-metal interactions.