Bimetallic Perthiocarbonate Complexes of Cobalt: Synthesis, Structure and Bonding.

The syntheses and structural elucidation of bimetallic thiolate complexes of early and late transition metals are described. Thermolysis of the bimetallic hydridoborate species [{CpCoPh}{-TePh}{-TeBH-Te,H}{CpCo}] (Cp* = -CMe) () in the presence of CS afforded the bimetallic perthiocarbonate complex [(CpCo)(-CS-S:S')(-S-S″:S‴)] () and the dithiolene complex [(CpCo)(-CS-S,S'] (). Complex contains a four-membered metallaheterocycle (CoS) comprising a perthiocarbonate [CS] unit and a disulfide [S] unit, attached opposite to each other. Complex was characterized by employing different multinuclear NMR, infrared spectroscopy, mass spectrometry, and single-crystal X-ray diffraction studies. Preliminary studies show that [Cp*VCl] () with an intermediate generated from CS and [LiBH·THF] yielded thiolate species, albeit different from the cobalt system. Furthermore, a computational analysis was performed to provide insight into the bonding of this bimetallic perthiocarbonate complex.