Insertion Reaction of Ketene into the Metal-Sulfur Bond:Synthesis and Characterization of [Cp_2Ln(mu-eta~1:eta~2-OC(SEt)=CPh_2)]_2 (Ln=Yb,Er,Sm,Y) and [Cp_2Er(mu-eta~2-OC(SEt)=CPhEt)]_2

摘要

Treatment of [Cp_2Ln(mu-SEt)]_2 with PhRC=C=O gives dimeric complexes [Cp_2Ln(mu-eta~1:eta~2-OC(SEt)=CPhR)]_2 [R=Ph,Ln=Yb (1),Er (2),Sm (3),Y (4);R=Et,Ln=Er (5)],which represent the first example of ketene insertion into a metal-sulfur bond and provide an efficient method for the synthesis of organolanthanides with a beta-thiolate-substituted enolate ligand.It is found that an excess of ketene does not affect the nature of the final complexes,with only a single insertion being observed.All these complexes are characterized by elemental analysis and spectroscopic properties.The structures of complexes l centre dot C_6H_5CH_3,2 centre dot C_6H_5CH_3,and 5 centre dot THF are determined through single-crystal X-ray diffraction analysis.