文献类型：期刊文献

中文题名：Insertion Reactions of PhEtCCO and PhNCO into Ln-S (Ln=Er, Y, Yb) Bond of [Cp_2Ln(μ-SEt)]_2

英文题名：Insertion reactions of PhEtCCO and PhNCO into Ln-S (Ln=Er, Y, Yb) bond of [Cp2Ln(μ-SEt)]2

作者：Zhang, Chunmei[1,2]; Lin, Yanghui[1]; Chen, Zhenxia[1]; Zhou, Xigeng[1]

机构：[1] Department of Chemistry, Fudan University, Shanghai 200433, China; [2] Department of Chemistry, East China University of Science and Technology, Shanghai 200237, China

年份：2006

卷号：24

期号：1

起止页码：9

中文期刊名：Journal of Rare Earths

外文期刊名：Journal of Rare Earths

收录：CSTPCD;;EI(收录号：2006229914343);Scopus;CSCD:【CSCD2011_2012】；

基金：ProjectsupportedbytheNationalNatutralScienceFoundationofChina(20372016)

语种：英文

中文关键词：organolanthanide; ketene; isocyanate; insertion;crystal structure

外文关键词：Characterization - Chemical reactions - Lanthanum compounds - Organic compounds - Synthesis (chemical)

摘要：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-η^1 ：η^3-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.
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)]2with PhEtCCO gives the α-thiolate-substituted enolate complexes [Cp2Ln (μ-η1:η3-OC(SEt)CPhEt)]2(Ln=Yb, Y), while [Cp2Ln(μ-SEt)]2react 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.