Insertion Reaction of Ketene into the Metal−Sulfur Bond:  Synthesis and Characterization of [Cp2Ln(μ-η1:η2-OC(SEt)CPh2)]2 (Ln = Yb, Er, Sm, Y) and [Cp2Er(μ-η1:η2-OC(SEt)CPhEt)]2

• Published in: Organometallics Vol. 23; no. 13; pp. 3246 - 3251
• Main Authors: Zhang, Chunmei, Liu, Ruiting, Zhou, Xigeng, Chen, Zhenxia, Weng, Linhong, Lin, Yanghui
• Format: Journal Article
• Language: English
• Published: American Chemical Society 21.06.2004
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/om049882r

Treatment of [Cp2Ln(μ-SEt)]2 with PhRCCO gives dimeric complexes [Cp2Ln(μ-η1:η2-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 β-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 1·C6H5CH3, 2·C6H5CH3, and 5·THF are determined through single-crystal X-ray diffraction analysis.