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  • Title: Synthesis of β-diketiminate-ligated bimetallic and monometallic lanthanide amide complexes and their reactivity with isoprene and AlMe3.
    Author: Sun S, Ouyang H, Luo Y, Zhang Y, Shen Q, Yao Y.
    Journal: Dalton Trans; 2013 Dec 14; 42(46):16355-64. PubMed ID: 24065074.
    Abstract:
    The amine elimination of lanthanide tris(amide) complexes with the phenylene-bridged bis(β-diketiminate) ligands PARA(Me)-H2, META(Me)-H2 and PARA(Pr)-H2 (PARA(Me)-H2 = 2[2,6-Me2C6H3NHC(Me)C(H)C(Me)N]-(para-phenylene), META(Me)-H2 = 2[2,6-Me2C6H3NHC(Me)C(H)C(Me)N]-(meta-phenylene), PARA(Pr)-H2 = 2[2,6-(i)Pr2C6H3NHC(Me)C(H)C(Me)N]-(para-phenylene)), and the mono-β-diketiminate ligand L(2,6-iPr2)Ph-H (2,6-(i)Pr2C6H3)NHC(Me)CHC(Me)N(C6H5)) afforded the bimetallic lanthanide amide complexes PARA(Me)-{Ln[N(SiMe3)2]2}2 (Ln = Y (1), Sm (2)), META(Me)-{Y[N(SiMe3)2]2}2 (3), PARA(Pr)-{Ln[N(HSiMe2)2]2}2 (Ln = Y (4), Sm (5)), and the monomeric complexes L(2,6-iPr2)Ph-Y[N(SiMe3)2]2 (6) and L(2,6-iPr2)Ph-Y[N(HSiMe2)2]2 (7). In the presence of AlR3 and on activation with 1 equiv. of [Ph3C][B(C6F5)4], complexes 1-7 showed a high activity toward the 1,4-selective polymerization of isoprene. The heterometallic Y/Al methyl complex [L(2,6-iPr2)Ph]Y[(μ-Me)2AlMe2]2 (8) was prepared to elucidate the real active precursor in the polymerization.
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