Salt metathesis reactions between pyridyl-methylene-cyclopentadienyl lithium salt and LnCl_3 followed by the addition of two equivalents of LiCH_2SiMe_3 afforded a series of constrained-geometry-configuration rare-ear...Salt metathesis reactions between pyridyl-methylene-cyclopentadienyl lithium salt and LnCl_3 followed by the addition of two equivalents of LiCH_2SiMe_3 afforded a series of constrained-geometry-configuration rare-earth metal bis(alkyl) complexes(Cp′CH_2-Py)Ln(CH_2SiMe_3)_2(THF)_n(Py = C_5H_4N, Cp′ = C_5H_4(Cp), Ln = Sc, n = 0(1); Cp′ = C_9H_6(Ind), Ln = Sc, n = 0(2); Cp′ = 3-Me_3Si-C_9H_5(3-Me_3Si-Ind), Ln = Sc, n = 0(3a), Ln = Lu(3b), Y(3c), n = 1; Cp′ = 2,7-(~tBu)_2C_(13)H_8(2,7-(~tBu)_2-Flu), Ln = Sc(4 a), n = 0, Ln = Lu(4b),Y(4c), n = 1) in moderate to good yields, which were characterized by NMR spectroscopy and single-crystal X-ray diffraction(for complex 3a). In the presence of [Ph_3C][B(C_6F_5)_4] and Al^iBu_3, these complexes displayed different performances towards styrene polymerization. Rare-earth metal bis(alkyl) precursors bearing Cp, Ind, and 3-Me_3Si-Ind segments exhibited very low catalytic activity to afford syndiotactic polystyrene. All electron-donating t Bu substituted complexes 4 a, 4 b, and 4 c showed very high activity and perfect syndiotactivity(rrrr > 99%), producing high molecular weight polystyrene(up to 54.1 × 10~4) with relatively narrow molecular distribution(PDI = 1.28-2.49).展开更多
The metathesis reaction between pyrrolidinyl-ethylene fluorenyl lithium salts with in situ prepared cationic rare-earth metal dialkyl species[Ln(CH_(2)SiMe_(3))_(2)(THF)_(x)][BPh_(4)]afford efficiently the correspondi...The metathesis reaction between pyrrolidinyl-ethylene fluorenyl lithium salts with in situ prepared cationic rare-earth metal dialkyl species[Ln(CH_(2)SiMe_(3))_(2)(THF)_(x)][BPh_(4)]afford efficiently the corresponding constrained-geometry complexes L^(1)Ln(CH_(2)SiMe_(3))_(2)(L^(1)=FluCH_(2)CH_(2)NC_(4)H_(8),Ln=Y(1a),Lu(1b),Sc(1c))and L^(2)Ln(CH_(2)SiMe_(3))_(2)(L^(2)=(2,7-di-tert-butyl)FluCH_(2)CH_(2)NC_(4)H_(8),Ln=Y(2a),Lu(2b),Sc(2c))in good yields.All these complexes were characterized by NMR spectroscopy,and the solid-state molecular structure of yttrium complex 1a was defined with single-crystal X-ray diffraction analysis.The catalytic performance of these complexes towards 2-vinylpyridine polymerization was investigated,where these complexes alone can efficiently promote the polymerization of 2-vinylpyridine giving isotactic poly(2-vinylpyridine).Upon the activation with[Ph_(3)C][B(C_(6)F_(5))_(4)],the yttrium and lutetium complexes also afford isotactic poly(2-vinylpyridine),while the scandium complexes produce syndiotactic poly(2-vinylpyridine).展开更多
基金financially supported by the National Natural Science Foundation of China (Nos. 51773193 and 21634007)department of science and technology of Jilin province (No.20180101171JC)the "973" project (No. 2015CB654702)
文摘Salt metathesis reactions between pyridyl-methylene-cyclopentadienyl lithium salt and LnCl_3 followed by the addition of two equivalents of LiCH_2SiMe_3 afforded a series of constrained-geometry-configuration rare-earth metal bis(alkyl) complexes(Cp′CH_2-Py)Ln(CH_2SiMe_3)_2(THF)_n(Py = C_5H_4N, Cp′ = C_5H_4(Cp), Ln = Sc, n = 0(1); Cp′ = C_9H_6(Ind), Ln = Sc, n = 0(2); Cp′ = 3-Me_3Si-C_9H_5(3-Me_3Si-Ind), Ln = Sc, n = 0(3a), Ln = Lu(3b), Y(3c), n = 1; Cp′ = 2,7-(~tBu)_2C_(13)H_8(2,7-(~tBu)_2-Flu), Ln = Sc(4 a), n = 0, Ln = Lu(4b),Y(4c), n = 1) in moderate to good yields, which were characterized by NMR spectroscopy and single-crystal X-ray diffraction(for complex 3a). In the presence of [Ph_3C][B(C_6F_5)_4] and Al^iBu_3, these complexes displayed different performances towards styrene polymerization. Rare-earth metal bis(alkyl) precursors bearing Cp, Ind, and 3-Me_3Si-Ind segments exhibited very low catalytic activity to afford syndiotactic polystyrene. All electron-donating t Bu substituted complexes 4 a, 4 b, and 4 c showed very high activity and perfect syndiotactivity(rrrr > 99%), producing high molecular weight polystyrene(up to 54.1 × 10~4) with relatively narrow molecular distribution(PDI = 1.28-2.49).
基金Project supported by National Natural Science Foundation of China(21805143)Natural Science Foundation of Zhejiang Province(LY21B040002)+1 种基金Natural Science Foundation of Ningbo(202003N4110)the K.C.Wong Magna Fund from Ningbo University。
文摘The metathesis reaction between pyrrolidinyl-ethylene fluorenyl lithium salts with in situ prepared cationic rare-earth metal dialkyl species[Ln(CH_(2)SiMe_(3))_(2)(THF)_(x)][BPh_(4)]afford efficiently the corresponding constrained-geometry complexes L^(1)Ln(CH_(2)SiMe_(3))_(2)(L^(1)=FluCH_(2)CH_(2)NC_(4)H_(8),Ln=Y(1a),Lu(1b),Sc(1c))and L^(2)Ln(CH_(2)SiMe_(3))_(2)(L^(2)=(2,7-di-tert-butyl)FluCH_(2)CH_(2)NC_(4)H_(8),Ln=Y(2a),Lu(2b),Sc(2c))in good yields.All these complexes were characterized by NMR spectroscopy,and the solid-state molecular structure of yttrium complex 1a was defined with single-crystal X-ray diffraction analysis.The catalytic performance of these complexes towards 2-vinylpyridine polymerization was investigated,where these complexes alone can efficiently promote the polymerization of 2-vinylpyridine giving isotactic poly(2-vinylpyridine).Upon the activation with[Ph_(3)C][B(C_(6)F_(5))_(4)],the yttrium and lutetium complexes also afford isotactic poly(2-vinylpyridine),while the scandium complexes produce syndiotactic poly(2-vinylpyridine).
