{(CPAM)Zr(Me)}{B(C₆F₅)₄} | 325699-79-4

• 英文名称: {(CPAM)Zr(Me)}{B(C₆F₅)₄}
• 英文别名: (η5-C5Me5)ZrMe[N(t-Bu)C(Me)N(Et)][B(C6F5)4]
• CAS: 325699-79-4
• 化学式: C₁₉H₃₅N₂Zr*C₂₄BF₂₀
• 分子量: 1061.77
• InChiKey: LODSOFVJQGVRDH-UHFFFAOYSA-N

反应信息

• 作为反应物：
  描述：

  {(CPAM)Zr(Me)}{B(C₆F₅)₄} 、 环戊烯 以 further solvent(s) 为溶剂， 生成
  参考文献：
  名称：

  Direct Observation of the Structural Isomerization of a Cationic Group 4 Ziegler−Natta Insertion Product

  摘要：

  An experimental model that allows for direct observation of a structural isomerization that is relevant to the group 4 metal-mediated Ziegler-Natta polymerization of alpha-olefins is presented. More specifically, several features of this system are consistent with current theories presented for chain epimerization that occurs during propene polymerization.

  DOI：

  10.1021/ja026820o
• 作为产物：
  描述：

  (η⁵-C₅Me₅)[N(Et)C(Me)N(tBu)]Zr(Me)₂ 、 N,N-二甲基苯铵四(五氟苯基)硼酸盐 以 氯苯 为溶剂， 生成 {(CPAM)Zr(Me)}{B(C₆F₅)₄}
  参考文献：
  名称：

  CPAM 环烷基甲基锆与异构 ω-烯基配合物的相对稳定性研究：环丁基甲基和环戊基甲基配合物的晶体结构

  摘要：

  环戊二烯基脒基 Zr 环烷基甲基配合物 (CPAM)Zr(X)[CH 2 ( cyclo -C m H 2m-1 )] (CPAM = (η 5 -C 5 ) 的合成、结构表征和相对稳定性的研究Me 5 )[( N,N ′)-κ 2 -N(Et)-C(Me)N( t -Bu)]) 对于 X = Cl 和 m = 3 ( 1a )、4 ( 1b ) 和 5 ( 1c ) 和 X = Me，m = 4 ( 2b )，以及对应的异构 ω-烯基配合物，(CPAM)Zr(Cl)[CH 2 (CH 2 ) n CH 2对于 n = 0 ( 3a )、1 ( 3b ) 和 2 ( 3c )，已经进行了CH = CH 2 ]。(CPAM)Zr(X)Cl (X = H 或 D) ( 8 ) 对亚甲基环丙烷的氢化锆化反应是通过 (CPAM)Zr(SiMe 2 Ph)Cl ( 7 )的 Zr-Si 键氢解原位生

  DOI：

  10.1016/j.poly.2022.116100
• 作为试剂：
  描述：

  在 {(CPAM)Zr(Me)}{B(C₆F₅)₄} 作用下， 以 氯苯 为溶剂， 反应 20.0h， 以124 mg的产率得到(η⁵-C₅Me₅)[N(Et)C(Me)N(tBu)]Zr(Cl)[CH₂(c-C₅H₉)]
  参考文献：
  名称：

  CPAM 环烷基甲基锆与异构 ω-烯基配合物的相对稳定性研究：环丁基甲基和环戊基甲基配合物的晶体结构

  摘要：

  环戊二烯基脒基 Zr 环烷基甲基配合物 (CPAM)Zr(X)[CH 2 ( cyclo -C m H 2m-1 )] (CPAM = (η 5 -C 5 ) 的合成、结构表征和相对稳定性的研究Me 5 )[( N,N ′)-κ 2 -N(Et)-C(Me)N( t -Bu)]) 对于 X = Cl 和 m = 3 ( 1a )、4 ( 1b ) 和 5 ( 1c ) 和 X = Me，m = 4 ( 2b )，以及对应的异构 ω-烯基配合物，(CPAM)Zr(Cl)[CH 2 (CH 2 ) n CH 2对于 n = 0 ( 3a )、1 ( 3b ) 和 2 ( 3c )，已经进行了CH = CH 2 ]。(CPAM)Zr(X)Cl (X = H 或 D) ( 8 ) 对亚甲基环丙烷的氢化锆化反应是通过 (CPAM)Zr(SiMe 2 Ph)Cl ( 7 )的 Zr-Si 键氢解原位生

  DOI：

  10.1016/j.poly.2022.116100

文献信息

• Goldilocks Effect of a Distal Substituent on Living Ziegler−Natta Polymerization Activity and Stereoselectivity within a Class of Zirconium Amidinate-Based Initiators
  作者：Yonghui Zhang、Erin K. Reeder、Richard J. Keaton、Lawrence R. Sita

  DOI：10.1021/om049835z

  日期：2004.7.1

  A new series of cationic zirconium amidinates, [(eta(5)-C5Me5)ZrMeN(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.