The synthesis and structural characterization of the molecular compound (μ3-benzene-1,2-dithiolato)hexacarbonylbis(μ3-1,1,1,4,4,4-hexafluorobut-2-ene-2,3-dithiolato)tricobaltmolybdenum, [Co3Mo(C4F6S2)2(C6H4S2)(CO)6] or Mo(tfd)2(bdt)(Co(CO)2)3 (tfd is 1,1,1,4,4,4-hexafluorobut-2-ene-2,3-dithiolate and bdt is benzene-1,2-dithiolate), are reported. The structure of the molecule contains the molybdenum tris(dithiolene) complex Mo(tfd)2(bdt) coordinated as a multidentate ligand to three cobalt dicarbonyl units. Each of the three cobalt centers is relatively close to molybdenum, with Co...Mo distances of 2.7224 (7), 2.8058 (7), and 2.6320 (6) Å. Additionally, each of the cobalt centers is bound via main-group donor atoms, but each one in a different way: the first cobalt atom is coordinated by two sulfur atoms from different dithiolenes (bdt and tfd). The second cobalt atom is coordinated by one sulfur from one tfd and two olefinic carbons from another tfd. The third cobalt is coordinated by one sulfur from bdt and two sulfurs from tfd. This is, to the best of our knowledge, the first structurally characterized example of a molybdenum (tris)dithiolene complex that coordinates to cobalt. The F atoms of two of the –CF3 groups were refined as disordered over two sets of sites with ratios of refined occupancies of 0.703 (7):0.297 (7) and 0.72 (2):0.28 (2).
Synthesis and structural characterization of inverse-coordination clusters from a two-electron superatomic copper nanocluster