[GdCl2(THF)2(((2,6-C6H3Et2)NHC(Me)CHC(Me)N(2,6-C6H3Et2))] | 1226516-10-4

• 英文名称: [GdCl2(THF)2(((2,6-C6H3Et2)NHC(Me)CHC(Me)N(2,6-C6H3Et2))]
• 英文别名: [GdCl2(tetrahydrofuran)2((2,6-C6H3Et2)NHC(Me)CHC(Me)N(2,6-C6H3Et2))]
• CAS: 1226516-10-4
• 化学式: C₃₃H₄₉Cl₂GdN₂O₂
• 分子量: 733.92
• InChiKey: GPTPTLXMBYIFDO-AEIVEMFJSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [GdCl2(THF)2(((2,6-C6H3Et2)NHC(Me)CHC(Me)N(2,6-C6H3Et2))] 、 三苯碳四(五氟苯基)硼酸盐 在 isoprene 、 Al(CH₃)3 作用下， 以 甲苯 为溶剂， 以38%的产率得到[((2,6-C6H3Et2)NHC(Me)CHC(Me)N(2,6-C6H3Et2))Gd3Cl3(THF)2][B(C6F5)4]]
  参考文献：
  名称：

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

  摘要：

  Lithiation of the beta-diketimines (2,6-C6H3R2)NH=C(Me)CH=C(Me)N(2,6-C6H3R2) (R = Me (HL1), Et (HL2)) by nBuLi was followed by metathesis reaction with LnCl(3)(THF)(x) and Y(BH4)(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)), (LGdCl2)-Gd-2(THF)2 (2), and (LY)-Y-1(BH4)(2)(THF) (8), respectively. Treatment of neutral HL1 with Y(CH2SiMe3)(3)(THF)(2) generated the bis(alkyl) complex 7, (LY)-Y-1(CH2SiMe3)(2)-(THF). Upon activation with [PhNHMe2][B(C6F5)(4)] and AliBu(3), complex 6 showed the highest cis1,4 selectivity (99.3%, T-p = 0 degrees 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 H-1 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.

  DOI：

  10.1021/om100100r
• 作为产物：
  描述：

  (2,6-diethylphenyl)NHC(CH3)CHC(CH3)N(2,6-diethylphenyl) 、 GdCl3(THF)4 在 n-C₄H₉Li 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以79%的产率得到[GdCl2(THF)2(((2,6-C6H3Et2)NHC(Me)CHC(Me)N(2,6-C6H3Et2))]
  参考文献：
  名称：

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

  摘要：

  Lithiation of the beta-diketimines (2,6-C6H3R2)NH=C(Me)CH=C(Me)N(2,6-C6H3R2) (R = Me (HL1), Et (HL2)) by nBuLi was followed by metathesis reaction with LnCl(3)(THF)(x) and Y(BH4)(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)), (LGdCl2)-Gd-2(THF)2 (2), and (LY)-Y-1(BH4)(2)(THF) (8), respectively. Treatment of neutral HL1 with Y(CH2SiMe3)(3)(THF)(2) generated the bis(alkyl) complex 7, (LY)-Y-1(CH2SiMe3)(2)-(THF). Upon activation with [PhNHMe2][B(C6F5)(4)] and AliBu(3), complex 6 showed the highest cis1,4 selectivity (99.3%, T-p = 0 degrees 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 H-1 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.

  DOI：

  10.1021/om100100r