Facile transformations of lanthanocene alkyls to lanthanocene thiolate, sulfide, and disulfide derivatives by reaction with elemental sulfur

Treatment of [Cp2Ln(μ-Me)]2 with 2 equiv of elemental sulfur in toluene at room temperature leads to the formation of the methylthiolate complexes [Cp2Ln(μ-SMe)]2 [ Ln = Yb (1a), Y (1b), Er (1c), Dy (1d)] in good yields. While reaction of Cp2Y(nBu) with elemental sulfur in 1:1 stoichiometric ratio under the same conditions yields [(Cp2Y)2(μ3-S)(THF)]2 (2a) as the metal-containing product with the extrusion of nBuSnBu and nBuSSnBu, the corresponding insertion intermediate [Cp2Y(μ-SnBu)]2 (1e) could be isolated only by decreasing the relative amount of S8 under more mild reaction conditions. Furthermore, [Cp2Yb(μ-SEt)]2 reacts with 2 equiv of sulfur to give a mixture of [(Cp2Yb)2(μ3-S)(THF)]2 (2b) and [Cp2Yb(THF)]2(μ-η2:η2-S2) (3). 2b and 3 can also be prepared from the reaction of [Cp2Yb(μ-Me)]2 with excess elemental sulfur in THF. All these results demonstrate that lanthanocene thiolate complexes are unstable in solution with S8, and the nature of the alkyl ligands and reaction conditions has a great infl...