Synthesis and structures of binuclear half-sandwich cobalt (III) ortho-carboranedithiolato complexes with silyl-bridged bis(cyclopentadienyl) ligands

Five binuclear half-sandwich cobalt complexes, [(η5-C5H4)Co(CO)I2]2SiMe2 (3), [(η5-C5H4)Co(S2C2B10H10)]2SiMe2 (4), [(η5-C5H4)]2Co2(μ2-S2C2B10H10)SiMe2 (5), [(η5-C5H3)CoI2](μ-I)[(η5-C5H3)Co(CO)I](SiMe2)2 (8), [(η5-C5H3)Co(S2C2B10H10)]2(SiMe2)2 (9), were successfully synthesized in moderate yield by the reactions of corresponding ligands, (C5H5)2SiMe2 (1) and (C5H4)2(SiMe2)2 (6), respectively. The molecular structures of 3, 5, 6, 8 and 9 was determined by X-ray crystallographic analysis, which distinctly depict various molecular structures containing the Cp rings and the metal centers with halide or 1,2-dicarba-closo-dodecaborane-1,2-dithiolato ligands. For the (η5-C5H4)2SiMe2 complexes, coordination of the fragments CpCo favors a exo conformation. With the rigid structure of the di-bridged ligand (C5H4)2(SiMe2)2, only cis isomers of the corresponding (η5-C5H3)2(Si2Me2)2 complexes are formed. All the complexes have been well characterized by elemental analysis, NMR and IR spectra.