(η⁵-C5Me5)ZrCl(SiMe2Ph)[t-BuNC(Me)NEt] | 583022-45-1

• 英文名称: (η⁵-C5Me5)ZrCl(SiMe2Ph)[t-BuNC(Me)NEt]
• CAS: 583022-45-1
• 化学式: C₂₆H₄₃ClN₂SiZr
• 分子量: 538.403
• InChiKey: XMOFFRUUKIMZBY-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(SiMe2Ph)[t-BuNC(Me)NEt] 、 氢气 以 正戊烷 为溶剂， 25.0 ℃ 、68.95 kPa 条件下， 生成 (η5-C5Me5)Zr(Cl)(H)[N(t-Bu)C(Me)N(Et)]
  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：

  反-2-丁烯 在 (η⁵-C5Me5)ZrCl(SiMe2Ph)[t-BuNC(Me)NEt] 、 氘 、 碘 作用下， 以 正戊烷 、 氘代苯 为溶剂， 20.0 ℃ 、206.84 kPa 条件下， 反应 4.17h， 生成 threo-3-d-2-iodobutane
  参考文献：
  名称：

  A Case for Asymmetric Hydrozirconation

  摘要：

  Hydrozirconation of cis-2-butene with Cp*ZrHCl[N(t-Bu)C(Me)N(Et)], generated in situ through hydrogenolysis of Cp*ZrCl(SiMe2Ph)[N(t-Bu)C(Me)N(Et)] (5), proceeds in high yield to produce a 1:2 mixture of the kinetically stable, diastereomeric sec-butyl complexes, 3a and 3b. Hydrozirconation of trans-2-butene under identical conditions provides a 2:1 mixture of 3a and 3b. Isolation of diastereomerically pure 3a was achieved through reaction of Cp*ZrCl2[N(t-Bu)C(Me)N(Et)] (4) with sec-butyllithium to provide a 2:1 ratio of 3a and 3b, followed by fractional crystallization. Crystallographic analysis of 3a establishes the relative configuration of the sec-butyl group with respect to the chiral zirconium center, thereby permitting construction of diastereomeric transition states that explain the origin of high face selectivity in the hydrozirconation of cis-2-butene. Finally, both iodinative zirconium-carbon bond cleavage and insertion of tert-butyl isocyanide into the zirconium-carbon bond of the sec-butyl group of 3a were found to proceed in high yield and with retention of the secondary alkyl structure. Together, these results provide a critical platform upon which efforts directed toward the asymmetric hydrozirconation of alkenes can be based.

  DOI：

  10.1021/ja0349453

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。
• End-Group-Confined Chain Walking within a Group 4 Living Polyolefin and Well-Defined Cationic Zirconium Alkyl Complexes for Modeling This Behavior
  作者：Matthew B. Harney、Richard J. Keaton、Lawrence R. Sita

  DOI：10.1021/ja0496975

  日期：2004.4.1

  Living polymers derived from the polymerization of 1-butene using the cationic zirconium initiator, Cp*ZrMe[N(Et)C(Me)-N(tBu)]}[B(C6F5)4] (Cp* = eta5-C5Me5) (1), have been shown to undergo end-group-confined chain walking that is competitive with direct beta-hydride elimination and chain release at -10 degrees C. The well-defined complexes, Cp*Zr(iBu)[N(Et)C(Me)N(tBu)]}[B(C6F5)4] (2) and Cp*Zr(2-ethylbutyl)[N(Et)C(Me)N(tBu)]}[B(C6F5)4] (3), were prepared, and each was found to possess a strong beta-hydrogen agostic interaction that is absent in the living polymer. The isotopically single- and double-labeled derivatives, Cp*Zr(2-d-2-methylpropyl)[N(Et)C(Me)N(tBu)]}[B(C6F5)4] (2') and Cp*Zr(1-13C-2-d-2-methylpropyl)[N(Et)C(Me)N(tBu)]}[B(C6F5)4] (2' '), were also prepared and found to undergo isotopic label scrambling at 0 degrees C. For 2' ', the observation that after scrambling each deuterium label is located on a 13C-labeled carbon atom is consistent with the Busico mechanism for chain-end epimerization rather than the Resconi mechanism. Decomposition of 3 yielded olefinic products also consistent with chain walking prior to beta-hydride elimination and chain release. Finally, the unexpected decrease in stability of the living polymer relative to that of the model complexes reveals the importance of subtle differences in steric and electronic factors in controlling beta-hydride elimination and chain release.