Synthesis and characterization of cyclopentadienyl thiolato complexes of magnesium

Treatment of Cp2Mg with 2-methyl-2-propanethiol, cyclohexanethiol, and 2-propanethiol in toluene at ambient temperature afforded the tetrameric cyclopentadienyl thiolato complexes [(η5-Cp)Mg(μ3-StBu)]4 (97%), [(η5-Cp)Mg(μ3-S(C6H11))]4 (92%), and [(η5-Cp)Mg(μ3-SiPr)]4 (83%) as colorless crystalline solids. Treatment of [(η5-Cp)Mg(μ3-StBu)]4 with tetrahydrofuran or tert-butylpyridine in dichloromethane/hexane afforded the dimeric solvated complexes [(η5-Cp)Mg(μ2-StBu)(THF)]2 (78%) or [(η5-Cp)Mg(μ2-StBu)(tBupy)]2 (60%) as colorless crystals. The crystal structures of [(η5-Cp)Mg(μ3-StBu)]4, [(η5-Cp)Mg(μ2-StBu)(THF)]2, and [(η5-Cp)Mg(μ2-StBu)(tBupy)]2 were determined by X-ray diffraction methods. In the solid-state structure, [(η5-Cp)Mg(μ3-StBu)]4 contains one η5-cyclopentadienyl ligand per magnesium and one cubic core of Mg4S4 that features a mirror plane of symmetry along one diagonal Mg2S2 plane. [(η5-Cp)Mg(μ2-StBu)(THF)]2 contains one η5-cyclopentadienyl ligand per magnesium and one bent Mg2S2 core with a mirror plane along thiolato bridges. [(η5-Cp)Mg(μ2-StBu)(tBupy)]2 contains one η5-cyclopentadienyl ligand per magnesium and a planar Mg2S2 core with a center of symmetry.