Reactions of 2-pyridinethiolate cobalt(III) complexes with pyridinethiolate or benzenethiolate ligands

Four half-sandwich cobalt complexes, Cp∗Co(2-PyS)2 (2), Cp∗Co(2-PyS)2 · HI (3), Cp∗Co(2-PyS) (4-PyS) (4), (Cp∗Co)2(μ-PhS)2(μ-2-PyS)I (5) [Cp∗ = pentamethylcyclopentadienyl, 2-PyS = 2-pyridinethiolate, 4-PyS = 4-pyridinethiolate, PhS = benzenethiolate] were successfully synthesized by the reactions of 2-pyridinethione, lithium 4-pyridinethiolate and lithium benzenethiolate with Cp∗Co(2-PyS)I (1), respectively. Complexes 2 and 3 have the structures with two 2-pyridinethiolates ligands coordinated to the cobalt atom. Two different pyridinethiolates ligands can be identified in complex 4. The molecular structure of 5 consists of two Cp∗–Co fragments, which are triply bridged by three sulfur atoms from different ligands. The molecular structures of 3 and 5 were determined by X-ray crystallographic analysis. All the complexes have been well characterized by elemental analysis, NMR and IR spectra.