(η5-C5Me4(SiMe3))′Dy(CH2SiMe3)2(thf) | 852043-81-3

• 英文名称: (η5-C5Me4(SiMe3))′Dy(CH2SiMe3)2(thf)
• 英文别名: Cp′Dy(CH₂SiMe₃)₂(thf)；(η⁵-C₅Me₄(SiMe₃))′Dy(CH₂SiMe₃)₂(thf)；(C5Me4SiMe3)Dy(CH2SiMe3)2(THF)
• CAS: 852043-81-3
• 化学式: C₂₄H₅₁DyOSi₃
• 分子量: 602.425
• InChiKey: LVZWPVMNLNQXAD-UHFFFAOYSA-N

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：

  (η5-C5Me4(SiMe3))′Dy(CH2SiMe3)2(thf) 、 苯硅烷 以 正己烷 为溶剂， 以70%的产率得到[(C5Me4SiMe3)Dy(μ-H)(CH2SiMe3)(THF)]2
  参考文献：
  名称：

  Rare-Earth-Metal Mixed Hydride/Aryloxide Complexes Bearing Mono(cyclopentadienyl) Ligands. Synthesis, CO₂ Fixation, and Catalysis on Copolymerization of CO₂ with Cyclohexene Oxide

  摘要：

  Hydrogenolysis of mono(cyclopentadienyl)-ligated rare-earth-metal bis(alkyl) complexes Cp'Ln-(CH2SiMe3)2(THF) (Ln = Y (1a), Dy (1b), Lu (1c); Cp' = C5Me4SiMe3) with PhSiH3 afforded the mixed hydride/alkyl complexes [Cp'Ln(mu-H)(CH2SiMe3)(THF)](2) (Ln = Y (2a), Dy (2b), Lu (2c)). The overall structure of complexes 2a-c is a C-2-symmetric dimer containing a planar symmetric Ln(2)H(2) core at the center of the molecule. Deprotonation of ArOH (Ar = C6H2-Bu-t(2)-2,6-Me-4) by the metal alkyl group of 2a-c led to formation of the mixed hydride/aryloxide derivatives [Cp'Ln(mu-H)(OAr)](2) (Ln = Y (3a), Dy (3b), Lu (3c)), which adopt the dimeric structure through hydride bridges with trans-accommodated terminal aryloxide groups. Complexes 3a-c swiftly reacted with CO2 to generate the mixed formate/carbonate complexes [Cp'Ln(mu-eta(1):eta(1)-O2CH)(mu-eta(1):eta(1)-O2COAr)](2) (Ln = Y (4a), Dy (4b), Lu (4c)). The two Cp'Ln fragments in these complexes are bridged by the formate and carbonate species, respectively, to form two square-pyramidal geometries around the metal centers. Furthermore, complexes 3a-c initiated the copolymerization of CO2 and cyclohexene oxide (CHO) under mild conditions to afford polymers with modest molecular weights and high carbonate linkages (92-99%).

  DOI：

  10.1021/om800170x
• 作为产物：
  描述：

  [(C5Me4SiMe3)Dy(μ-H)(CH2SiMe3)(THF)]2 以 四氢呋喃 为溶剂， 生成 (η5-C5Me4(SiMe3))′Dy(CH2SiMe3)2(thf)
  参考文献：
  名称：

  Rare-Earth-Metal Mixed Hydride/Aryloxide Complexes Bearing Mono(cyclopentadienyl) Ligands. Synthesis, CO₂ Fixation, and Catalysis on Copolymerization of CO₂ with Cyclohexene Oxide

  摘要：

  Hydrogenolysis of mono(cyclopentadienyl)-ligated rare-earth-metal bis(alkyl) complexes Cp'Ln-(CH2SiMe3)2(THF) (Ln = Y (1a), Dy (1b), Lu (1c); Cp' = C5Me4SiMe3) with PhSiH3 afforded the mixed hydride/alkyl complexes [Cp'Ln(mu-H)(CH2SiMe3)(THF)](2) (Ln = Y (2a), Dy (2b), Lu (2c)). The overall structure of complexes 2a-c is a C-2-symmetric dimer containing a planar symmetric Ln(2)H(2) core at the center of the molecule. Deprotonation of ArOH (Ar = C6H2-Bu-t(2)-2,6-Me-4) by the metal alkyl group of 2a-c led to formation of the mixed hydride/aryloxide derivatives [Cp'Ln(mu-H)(OAr)](2) (Ln = Y (3a), Dy (3b), Lu (3c)), which adopt the dimeric structure through hydride bridges with trans-accommodated terminal aryloxide groups. Complexes 3a-c swiftly reacted with CO2 to generate the mixed formate/carbonate complexes [Cp'Ln(mu-eta(1):eta(1)-O2CH)(mu-eta(1):eta(1)-O2COAr)](2) (Ln = Y (4a), Dy (4b), Lu (4c)). The two Cp'Ln fragments in these complexes are bridged by the formate and carbonate species, respectively, to form two square-pyramidal geometries around the metal centers. Furthermore, complexes 3a-c initiated the copolymerization of CO2 and cyclohexene oxide (CHO) under mild conditions to afford polymers with modest molecular weights and high carbonate linkages (92-99%).

  DOI：

  10.1021/om800170x

文献信息

• Cyclopentadienyl-Like Ligand as a Reactive Site in Half-Sandwich Bis(amidinato) Rare-Earth-Metal Complexes: An Efficient Application in Catalytic Addition of Amines to Carbodiimides
  作者：Peng-Hui Wei、Ling Xu、Li-Cheng Song、Wen-Xiong Zhang、Zhenfeng Xi

  DOI：10.1021/om5002793

  日期：2014.6.9

  excellent catalytic activity for the addition of amines to carbodiimides, yielding the corresponding guanidines. Isolation, structural characterization, and catalytic application of the binuclear lutetium amido complex showed clearly that the catalytic cycle was initiated by the dissociation of Cp′. These results demonstrated that Cp′, for the first time, acted as a reactive site to yield the active Ln–N

  一系列混合CP的'/双（amidinato）（CP'=η 5 -C 5我4（森达3））镧系络合物通过1合成：CP'Ln（CH 2之间的酸-碱反应2森达3）2（THF）（Ln为Y，镝，铒，Lu）和脒。这些CP'/双（amidinato）络合物显示出优异的催化活性的加成胺制碳二亚胺，得到相应的胍。双核酰胺配合物的分离，结构表征和催化应用清楚地表明，催化循环是由CP'的解离引发的。这些结果表明，CP'，对于第一次，充当反应部位产生活性LN-N物种。