[(η5-C5Me5)ZrCl(iso-butyl)(EtNC(Me)N-t-Bu)] | 590369-38-3

• 英文名称: [(η5-C5Me5)ZrCl(iso-butyl)(EtNC(Me)N-t-Bu)]
• CAS: 590369-38-3
• 化学式: C₂₂H₄₁ClN₂Zr
• 分子量: 460.258
• InChiKey: HUWWGDLKSRLTHV-UHFFFAOYSA-M

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-C5Me5)ZrCl(iso-butyl)(EtNC(Me)N-t-Bu)] 、 [(η5-C5Me5)Zr(i-Bu)[N(Et)C(Me)N(t-Bu)]][B(C6F5)4] 以 further solvent(s) 为溶剂， 生成
  参考文献：
  名称：

  通过活性位点和休眠位点之间快速可逆的氯化物退化转移进行立体特异性活性齐格勒-纳塔聚合

  摘要：

  成功实现立体定向氯化物退化转移活性齐格勒-纳塔聚合工艺，提供窄多分散性 (Mw/Mn) 的全同立构聚烯烃

  DOI：

  10.1021/ja0492889
• 作为产物：
  描述：

  [(η5-C5Me5)ZrCl(tert-butyl)(EtNC(Me)N-t-Bu)] 以 not given 为溶剂， 以0%的产率得到[(η5-C5Me5)ZrCl(iso-butyl)(EtNC(Me)N-t-Bu)]
  参考文献：
  名称：

  Regarding the Stability of d⁰ Monocyclopentadienyl Zirconium Acetamidinate Complexes Bearing Alkyl Substituents with β-Hydrogens

  摘要：

  The monocyclopentadienyl zirconium acetamidinate complexes, (eta(5)-C(5)Me(5))Zr[N(R(1))C(Me)N(R(2))]R(3)R(4) (1-8), have been shown to be remarkably resistant to beta-hydrogen eliminations/abstractions, including the tert-butyl derivative, 3 (R(1) = R(2) = Cy, R(3) = t-Bu, R(4) = Cl), which resists both decomposition and isomerization in solution to temperatures of at least 100 degrees C. Further, two striking examples of an apparent preference for alternative hydrogen-atom abstractions in which complexes 1 and 7/8 that bear isomeric dibutyl substituents are transformed at elevated temperatures to complexes 9 and 10/11 that contain the isomeric butadiene and trimethylenemethane (TMM) C(4) fragments, respectively, are presented. These results serve to not only introduce a new ligand environment for zirconium in which beta-hydrogen elimination/abstraction processes are substantially retarded, but they further document the availability of alternative low-energy hydrogen abstraction pathways for group 4 alkyl complexes.

  DOI：

  10.1021/ja017294o

文献信息

• Living Ziegler−Natta Polymerization by Early Transition Metals:  Synthesis and Evaluation of Cationic Zirconium Alkyl Complexes Bearing β-Hydrogens as Models for Propagating Centers
  作者：Matthew B. Harney、Richard J. Keaton、James C. Fettinger、Lawrence R. Sita

  DOI：10.1021/ja057866v

  日期：2006.3.1

  zirconium and hafnium complexes with alkyl substituents bearing beta-hydrogens of general formula (eta(5)-C5Me5)MR[N(Et)C(Me)N(t-Bu)]}[B(C6F5)4] [M = Zr; R = Et, n-Pr, i-Pr, n-Bu, i-Bu, and 2-ethylbutyl (5a-f) and M = Hf; R = i-Bu and t-Bu (6 and 7, respectively)] is described, including several isotopically labeled derivatives. The ability of these complexes to serve as model complexes for the living Ziegler-Natta

  一系列带有通式 (eta(5)-C5Me5)MR[N(Et)C(Me)N(t-Bu)]} 的带有 β-氢的烷基取代基的阳离子锆和铪配合物的合成和表征[B(C6F5)4] [M = Zr; R = Et、n-Pr、i-Pr、n-Bu、i-Bu 和 2-乙基丁基 (5a-f)，M = Hf；描述了 R = i-Bu 和 t-Bu（分别为 6 和 7）]，包括几种同位素标记的衍生物。这些配合物作为烯烃的活性齐格勒-纳塔聚合反应的模型配合物的能力已经得到解决，该聚合反应可以使用引发剂 2a (R = Me in 5) 进行。获得的结果进一步阐明了空间和电子因素，这些因素可能有助于基于早期过渡金属引发剂的齐格勒-纳塔聚合的活性特性。
• Degenerative Transfer Living Ziegler−Natta Polymerization:  Application to the Synthesis of Monomodal Stereoblock Polyolefins of Narrow Polydispersity and Tunable Block Length
  作者：Yonghui Zhang、Richard J. Keaton、Lawrence R. Sita

  DOI：10.1021/ja029780x

  日期：2003.7.1

  transfer involving rapid and reversible methyl group exchange between cationic (active) zirconium propagating centers and neutral (dormant) methyl, polymeryl zirconium end groups. Facile metal-centered epimerization of the dormant species is responsible for a loss of stereocontrol during propagation that produces iso-rich material in contrast to the pure isotactic polymer microstructure obtained when degenerative

  中性二甲基五甲基环戊二烯基乙脒酸锆 (eta(5)-C(5)Me(5))ZrMe(2)[N(t-Bu)C(Me)N(Et)] 可作为高活性引发剂当通过亚化学计量量的硼酸盐 [PhNMe(2)H][B(C(C()) 单去甲基化“活化”时，α-烯烃的活性齐格勒-纳塔聚合反应生成窄多分散性 (D < 或 = 1.05) 的聚烯烃6)F(5))(4)]。这种活性聚合进行的机制是通过退化转移过程，涉及阳离子（活性）锆增长中心和中性（休眠）甲基、聚合基锆端基之间的快速和可逆甲基交换。与不存在退化转移时获得的纯全同立构聚合物微观结构相比，休眠物种的容易的以金属为中心的差向异构化导致在传播过程中失去立体控制，从而产生富含等规的材料。通过在连续的单体聚合之间“开启”和“关闭”退化转移，已经证明了生产窄多分散性和可调节嵌段长度的单峰立体嵌段聚烯烃的成功策略。