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 [{Cp*CoPh}{ µ -TePh}{ µ -TeBH 3 - ĸ 2 Te,H}{Cp*Co}] (Cp* = ɳ 5 -C 5 Me 5 ) ( 1 ) in the presence of CS 2 afforded the bimetallic perthiocarbonate complex [(Cp*Co) 2 ( μ -CS 4 - κ 1 S: κ 2 S')( μ -S 2 - κ 2 S″: κ 1 S‴)] ( 2 ) and the dithiolene complex [(Cp*Co)( μ -C 3 S 5 - κ 1 S,S'] ( 3 ). Complex 2 contains a four-membered metallaheterocycle (Co 2 S 2 ) comprising a perthiocarbonate [CS 4 ] 2- unit and a disulfide [S 2 ] 2- unit, attached opposite to each other. Complex 2 was characterized by employing different multinuclear NMR, infrared spectroscopy, mass spectrometry, and single-crystal X-ray diffraction studies. Preliminary studies show that [Cp*VCl 2 ] 3 ( 4 ) with an intermediate generated from CS 2 and [LiBH 4 ·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.