β-Diketiminato Rare-Earth Metal Complexes. Structures, Catalysis, and Active Species for Highly cis-1,4-Selective Polymerization of Isoprene

Lithiation of the β-diketimines (2,6-C 6 H 3 R 2 )NH═C(Me)CH═C(Me)N(2,6-C 6 H 3 R 2 ) (R = Me (HL 1 ), Et (HL 2 )) by n BuLi was followed by metathesis reaction with LnCl 3 (THF) x and Y(BH 4 ) 3 (THF) 2 to afford the corresponding complexes L 1 LnCl 2 (THF) 2 (Ln = Gd ( 1 ), Nd ( 3 ), Dy ( 4 ), Er ( 5 ), Y ( 6 )), L 2 GdCl 2 (THF) 2 ( 2 ), and L 1 Y(BH 4 ) 2 (THF) ( 8 ), respectively. Treatment of neutral HL 1 with Y(CH 2 SiMe 3 ) 3 (THF) 2 generated the bis(alkyl) complex 7, L 1 Y(CH 2 SiMe 3 ) 2 (THF). Upon activation with [PhNHMe 2 ][B(C 6 F 5 ) 4 ] and Al i Bu 3, complex 6 showed the highest cis -1,4 selectivity (99.3%, T p = 0 °C) toward the polymerization of isoprene, while complex 7 had a comparatively low cis -1,4 selectivity, and in contrast, complex 8 was completely inert. The influences of the ortho substituents of the N-aryl rings of the ligands, the types of central metals and cocatalysts, and addition sequence of the catalyst components had been thoroughly investigated. By means of X-ray diffraction and 1 H NMR spectroscopy analyses, the intermediates arising from the stoichiometric reactions among the catalyst components and the probable active species were elucidated, which facilitates further investigation of the mechanism for diene polymerization.