Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Dushu Lake Campus, Soochow University, Suzhou 215123, People's Republic of China.
Dalton Trans. 2013 Dec 14;42(46):16355-64. doi: 10.1039/c3dt52014e.
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.
具有亚苯基桥联双（β-二酮亚胺）配体 PARA(Me)-H2、META(Me)-H2 和 PARA(Pr)-H2（PARA(Me)-H2=2[2,6-Me2C6H3NHC(Me)C(H)C(Me)N]-(para- 苯），META(Me)-H2=2[2,6-Me2C6H3NHC(Me)C(H)C(Me)N]-(meta-苯），PARA(Pr)-H2=2[2,6-(i)Pr2C6H3NHC(Me)C(H)C(Me)N]-(para- 苯））和单-β-二酮亚胺配体 L(2,6-iPr2)Ph-H（2,6-(i)Pr2C6H3）NHC(Me)CHC(Me)N(C6H5))合成了双金属镧系酰胺配合物 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））和单体配合物 L(2,6-iPr2)Ph-Y[N(SiMe3)2]2（6）和 L(2,6-iPr2)Ph-Y[N(HSiMe2)2]2（7）。在 AlR3 的存在下，并用 1 当量的[Ph3C][B(C6F5)4]激活，配合物 1-7 对异戊二烯的 1,4-选择性聚合表现出很高的活性。制备了杂金属 Y/Al 甲基配合物[L(2,6-iPr2)Ph]Y[(μ-Me)2AlMe2]2（8），以阐明聚合中的真正活性前体。
