([N,N-2,6-diisopropylphenyl-2,4-pentanediimine(1-)]YbCl(μ-Cl)3[N,N-2,6-diisopropylphenyl-2,4-pentanediimine(1-)](THF)) | 405885-06-5

• 英文名称: ([N,N-2,6-diisopropylphenyl-2,4-pentanediimine(1-)]YbCl(μ-Cl)3[N,N-2,6-diisopropylphenyl-2,4-pentanediimine(1-)](THF))
• 英文别名: [(N,N'-bis(2,6-diisopropylphenyl)-2,4-pentanediiminato(1-))2Yb2Cl(μ-Cl)3(THF)]；[((DIPPh)2nacnac)2Yb2Cl4(THF)]
• CAS: 405885-06-5
• 化学式: C₆₂H₉₀Cl₄N₄OYb₂
• 分子量: 1395.31
• InChiKey: JGOANXZHTTUUFB-PSHXKUAASA-J

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
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• 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：

  乙二醇二甲醚 、 ([N,N-2,6-diisopropylphenyl-2,4-pentanediimine(1-)]YbCl(μ-Cl)3[N,N-2,6-diisopropylphenyl-2,4-pentanediimine(1-)](THF)) 以 乙二醇二甲醚 、 甲苯 为溶剂， 以83%的产率得到[N,N-2,6-diisopropylphenyl-2,4-pentanediimine(1-)]YbCl2(DME)
  参考文献：
  名称：

  Synthesis and Structural Characterization of β-Diketiminate−Lanthanide Amides and Their Catalytic Activity for the Polymerization of Methyl Methacrylate and ε-Caprolactone

  摘要：

  The synthesis and catalytic activity of lanthanide monoamido complexes supported by a beta-diketiminate ligand are described. Donor solvents, such as DME, can cleave the chloro bridges of the dinuclear beta-diketiminate ytterbium dichloride {[(DIPPh)(2)nacnac]YbCl(mu-Cl)(3)Yb[(DIPPh)(2)nacnac](THF)} (1) [(DIPPh)(2)nacnac = N,N-diisopropylphenyl-2,4-pentanediimine anion] to produce the monomeric complex [(DIPPh)(2)nacnac]YbCl2(DME) (2) in high isolated yield. Complex 2 is a useful precursor for the synthesis of beta-diketiminate-ytterbium monoamido derivatives. Reaction of complex 2 with 1 equiv of LiNPr2i in THF at room temperature, after crystallization in THF/toluene mixed solvent, gave the anionic beta-diketiminate-ytterbium amido complex [(DIPPh)(2)nacnac]Yb(NPr2i)(mu-Cl)(2)Li(THF)(2) (3), while similar reaction of complex 2 with LiNPh2 produced the neutral complex [(DIPPh)(2)nacnac]Yb(NPh2)Cl(THF) (4). Recrystallization of complex 3 from toluene solution at elevated temperature led to the neutral beta-diketiminate-lanthanide amido complex [{(DIPPh)(2)nacnac}Yb(NPr2i)(mu-Cl)](2) (5). The reaction medium has a significant effect on the outcome of the reaction. Complex 2 reacted with 1 equiv of LiNPr2i and LiNC5H10 in toluene to produce directly the neutral beta-diketiminate-lanthanide amido complexes 5 and [{(DIPPh)(2)nacnac}Yb(NC5H10)(THF)(mu-Cl)](2) (6), respectively. These complexes were well characterized, and their crystal structures were determined, Complexes 4-6 exhibited good catalytic activity for the polymerization of methyl methacrylate and c-caprolactone.

  DOI：

  10.1021/ic051158t

文献信息

• Controlled synthesis of mononuclear or binuclear aryloxo ytterbium complexes supported by β-diketiminate ligand and their activity for polymerization of ε-caprolactone and L-lactide
  作者：Hongxia Chen、Peng Liu、Haisheng Yao、Yong Zhang、Yingming Yao、Qi Shen

  DOI：10.1039/c002385j

  日期：——

  The reaction of monomeric [(DIPPh)2nacnac]YbCl2(THF)2 ((DIPPh)2nacnac = N,N-diisopropylphenyl-2,4-pentanediimineanion) with NaOAr (OAr = 2,6-diisopropylphenoxide) in THF afforded the mononuclear complexes [(DIPPh)2nacnac]Yb(OAr)Cl(THF) 1 and [(DIPPh)2nacnac]Yb(OAr)22 depending on the molar ratio of dichloride to sodium salt, while the same reaction with NaOAr′ (OAr′ = 2,6-dimethylphenoxide) in toluene yielded the binuclear complex [(DIPPh)2nacnac}Yb(OAr′)]2(μ-Cl)23. Treatment of [(DIPPh)2nacnac]Yb(THF)(μ-Cl)3Yb(Cl)[(DIPPh)2nacnac] with NaOAr and NaOAr′, respectively, in toluene yielded selectively the corresponding binuclear complexes [(DIPPh)2nacnac]Yb(OAr)(μ-Cl)3Yb[(DIPPh)2nacnac](THF)} 4 and [(DIPPh)2nacnac]Yb(OAr′)(μ-Cl)3Yb[(DIPPh)2nacnac](THF)} 5 in high yields. All complexes were structurally characterized. Complex 2 was found to be a highly active initiator for both polymerizations of ε-caprolactone (ε-CL) and L-lactide. All monoaryloxide complexes can initiate the polymerization of ε-CL in a controlled manner giving polymers with narrow molecular weight distributions (Mw/Mn around 1.06) with relatively low activity relative to complex 2.

  单核[(DIPPh)2nacnac]YbCl2(THF)2（(DIPPh)2nacnac = N,N-二异丙基苯基-2,4-戊二亚胺离子）与 NaOAr（OAr = 2、6-二异丙基苯氧化物）在 THF 中的反应，根据二氯化物与钠盐的摩尔比，得到了单核络合物 [(DIPPh)2nacnac]Yb(OAr)Cl(THF) 1 和 [(DIPPh)2nacnac]Yb(OAr)22 、而在甲苯中与 NaOArâ²（OArâ² = 2,6-二甲基苯氧化物）进行同样的反应，则可生成双核络合物 [(DIPPh)2nacnac}Yb(OArâ²)]2(δ-Cl)23。分别用 NaOAr 和 NaOArâ² 处理[(DIPPh)2nacnac]Yb(THF)(δ-Cl)3Yb(Cl)[(DIPPh)2nacnac]、在甲苯中选择性地得到相应的双核配合物 [(DIPPh)2nacnac]Yb(OAr)(δ-Cl)3Yb[(DIPPh)2nacnac](THF)}4 和 [(DIPPh)2nacnac]Yb(OArâ²)(δ-Cl)3Yb[(DIPPh)2nacnac](THF)}5 ，产量很高。所有络合物都具有结构特征。研究发现，络合物 2 对 ε-Caprolactone (ε-CL)和 L-内酰胺的聚合都有很高的引发活性。所有单芳基氧化物络合物都能以受控方式引发 ε-CL 的聚合反应，生成分子量分布较窄（Mw/Mn 约为 1.06）的聚合物，但活性相对络合物 2 较低。