Amine Elimination Reactions between Homoleptic Silylamide Lanthanide Complexes and an Isopropylidene-Bridged Cyclopentadiene−Fluorene System
作者:Aswini K. Dash、Abbas Razavi、André Mortreux、Christian W. Lehmann、Jean-François Carpentier
DOI:10.1021/om0200398
日期:2002.7.1
unsymmetrical ligand C5H5-CMe2-C13H9 (CpH-CMe2-FluH) onto group III-metal centers (Y, La, Nd) to give in turn the neutral, ate-complex-free ansa-lanthanidocenes. The reactions of homoleptic Ln[N(SiMe3)2]3 (Ln = Y (1), La (2), Nd (3)) with CpH-CMe2-FluH (4) in THF under mild conditions lead to the formation of ansa-complexes (η5,η5-Cp-CMe2-Flu)Ln(η5-Cp-CMe2-FluH) (Ln = Y (8), La (12), Nd (13)) in 70−84%
这一贡献描述了胺消除过程,这是将异亚丙基桥连的不对称配体C 5 H 5 -CMe 2 -C 13 H 9(CpH-CMe 2 -FluH)引入到III类金属中心的传统盐复分解反应的另一种合成途径。(Y,镧,钕),以轮流中性给,吃了复杂的无柄-lanthanidocenes。均质Ln [N(SiMe 3)2 ] 3(Ln = Y(1),La(2),Nd(3))与CpH-CMe 2 -FluH(4)的反应)在温和的条件下THF导致形成柄-complexes(η 5,η 5 -Cp-CME 2 -Flu)LN(η 5 -Cp-CME 2 -FluH)(Ln为Y(8),LA(12),Nd(13))的分离产率为70-84%(基于4)。这些反应通过快速形成双继续进行(酰氨基)镧系元素的中间体(η 5 -Cp-CME 2 -FluH)LN [N(森达3)2 ] 2(Ln为Y(5),拉(9)),其经历容易