Insertion Reactions of PhEtCCO and PhNCO into Ln-S (Ln = Er, Y, Yb) Bond of [Cp2Ln(μ-SEt)]2

The reactivity of lanthanocene thiolates [Cp2Ln(μ-SEt)]2(Ln = Er, Y, Yb) with PhEtCCO and with PhNCO was examined. Treatment of [Cp2Ln(μ-SEt)]2 with PhEtCCO gives the α-thiolate-substituted enolate complexes [Cp2Ln (μ-η1:η3-OC(SEt)CPhEt)]2(Ln = Yb, Y), while [Cp2Ln(μ-SEt)]2 react with PhNCO to give the lanthanocene amido derivatives [Cp2Ln(OC(SEt)NPh)]2(Ln = Er, Yb). In both cases, the insertion reaction is independent of the stoichiometric ratio and the nature of lanthanides, demonstrating that lanthanocene thiolates are high reactive toward PhEtCCO and PhNCO under the conditions involved. All complexes are characterized by elemental analysis and spectroscopic properties, of which the structures of ytterbium enolate and erbium amido are also determined by X-ray single crystal diffraction analysis, indicating that both of them are centrosymmetric binuclear structures.