(η5-C5Me5)ZrCl2[N(t-Bu)C(t-Bu)N(Et)] | 728949-30-2

• 英文名称: (η5-C5Me5)ZrCl2[N(t-Bu)C(t-Bu)N(Et)]
• CAS: 728949-30-2
• 化学式: C₂₁H₃₈Cl₂N₂Zr
• 分子量: 480.676
• InChiKey: CYOFESUFOFFGHR-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• 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)ZrCl2[N(t-Bu)C(t-Bu)N(Et)] 、 甲基锂 以 乙醚 为溶剂， 以70%的产率得到(η5-C5Me5)ZrMe2[N(t-Bu)C(t-Bu)N(Et)]
  参考文献：
  名称：

  Goldilocks Effect of a Distal Substituent on Living Ziegler−Natta Polymerization Activity and Stereoselectivity within a Class of Zirconium Amidinate-Based Initiators

  摘要：

  A new series of cationic zirconium amidinates, [(eta(5)-C5Me5)ZrMe{N(Et)C(R-3)N(Bu-t)}]- [B(C6F5)(4)] (R-3 = Me, H, Ph, and Bu-t) (1a-d), were synthesized and their ability to function as initiators for the stereoselective living Ziegler-Natta polymerization of 1-hexene evaluated. Whereas la is highly active for the isospecific living polymerization of 1-hexene as previously reported, polymerizations conducted with 1b and 1c both display a significant loss of stereocontrol, and in the case of 1b, the polymerization is no longer living. Further, 1d was found to be inactive for polymerization. The Golidlocks effect observed for the distal R3 substituent in this series, i.e., 1b "too small", 1c "too large", 1a "just right", appears to be steric in origin. Solution and solid state structural studies suggest, however, that two different mechanisms are most likely operative for the loss of stereocontrol observed for 1b and 1c: a low barrier to metal-centered epimerization in the case of 1b and a lack of steric discrimination at the metal center for olefin binding in the case of 1c.

  DOI：

  10.1021/om049835z
• 作为产物：
  描述：

  pentamethylcyclopentadienylzirconium(IV) trichloride 、 1-叔丁基-3-乙基碳二亚胺 、 叔丁基锂 以 乙醚 、 环戊烷 为溶剂， 生成 (η5-C5Me5)ZrCl2[N(t-Bu)C(t-Bu)N(Et)]
  参考文献：
  名称：

  Goldilocks Effect of a Distal Substituent on Living Ziegler−Natta Polymerization Activity and Stereoselectivity within a Class of Zirconium Amidinate-Based Initiators

  摘要：

  A new series of cationic zirconium amidinates, [(eta(5)-C5Me5)ZrMe{N(Et)C(R-3)N(Bu-t)}]- [B(C6F5)(4)] (R-3 = Me, H, Ph, and Bu-t) (1a-d), were synthesized and their ability to function as initiators for the stereoselective living Ziegler-Natta polymerization of 1-hexene evaluated. Whereas la is highly active for the isospecific living polymerization of 1-hexene as previously reported, polymerizations conducted with 1b and 1c both display a significant loss of stereocontrol, and in the case of 1b, the polymerization is no longer living. Further, 1d was found to be inactive for polymerization. The Golidlocks effect observed for the distal R3 substituent in this series, i.e., 1b "too small", 1c "too large", 1a "just right", appears to be steric in origin. Solution and solid state structural studies suggest, however, that two different mechanisms are most likely operative for the loss of stereocontrol observed for 1b and 1c: a low barrier to metal-centered epimerization in the case of 1b and a lack of steric discrimination at the metal center for olefin binding in the case of 1c.

  DOI：

  10.1021/om049835z