Zr(PhN(CH2)3NPh)Cl2(THF)2 | 299410-33-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Zr(PhN(CH2)3NPh)Cl2(THF)2
• 英文别名: ZrCl2(THF)2(PhN(CH2)3NPh)；oxolane;phenyl(3-phenylazanidylpropyl)azanide;zirconium(4+);dichloride
• CAS: 299410-33-6
• 化学式: C₂₃H₃₂Cl₂N₂O₂Zr
• 分子量: 530.649
• InChiKey: CYZJWRNFDGCSKX-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  7.76
• 重原子数：
  30
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  20.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  、 Zr(PhN(CH2)3NPh)Cl2(THF)2 以 乙醚 为溶剂， 生成 meso-Me2Si(3-(1-Me-Cy)-C5H3)2Zr(PhN(CH2)3NPh)
  参考文献：
  名称：

  通过环戊二烯基和氯化物配体的可逆交换控制 ansa-Zirconocene 立体化学

  摘要：

  Li2[Me2Si(3-R-C5H3)2]盐与Zr{Me3SiN(CH2)3NSiMe3}Cl2(THF)2在THF中反应定量得到外消旋Me2Si(3-R-C5H3)2Zr{Me3SiN(CH2)具有 100% 立体选择性的 3NSiMe3} 锆茂。核磁共振监测研究表明，这些反应最初形成外消旋/内消旋混合物，经过异构化成为纯外消旋。异构化需要 Cp-enantioface 交换，并由氯离子催化，从 Me2Si(3-R-C5H3)2Zr{Me3SiN(CH2)3NSiMe3} 可逆地置换 Cp-。所选配合物的动力学分析显示异构化速率对茂金属和氯化物浓度的一级依赖性。可逆 Cp-/Cl- 交换对于 {ansa-bis-Cp}ZrCl2 和非桥连 Cp2ZrCl2 复合物也很容易。

  DOI：

  10.1021/ja0681523
• 作为产物：
  描述：

  、 氯化锆(IV) 以 四氢呋喃 、 乙醚 为溶剂， 以>99的产率得到Zr(PhN(CH2)3NPh)Cl2(THF)2
  参考文献：
  名称：

  外消旋 Me2Si 桥接双（茚基）锆茂配合物的一般合成

  摘要：

  DOI：

  10.1021/ja001005z

文献信息

• Syntheses of rac/meso-{PhP(3-t-Bu-C5H3)2}-Zr{RN(CH2)3NR}, structural analyses of rac-{PhP(3-t-Bu-C5H3)2}Zr{RN(CH2)3NR} (where R is SiMe3 or Ph), and meso to rac isomerization
  作者：Jonathan C. Axtell、Susan D. Thai、Laurel A. Morton、William S. Kassel、William G. Dougherty、Deanna L. Zubris

  DOI：10.1016/j.jorganchem.2008.09.018

  日期：2008.12

  ZrRN(CH2)3NR}Cl2(THF)2 (where R = SiMe3 or Ph, respectively) using ethereal solvent. These isomeric pairs were characterized by 1H, 13C1H}, and 31P1H} NMR spectroscopy; rac-3 and rac-4 were also examined via single crystal X-ray crystallography. The structures of rac-3 and rac-4 are notable in the tendency of the cyclopentadienyl rings towards η3 coordination. While isolated samples of rac-3/meso-3 and rac-4/meso-4

  的合成外消旋/内消旋- PHP（3-吨-Bu-C 5 H ^ 3）2 } Zr的我3的SiN（CH 2）3 NSiMe 3 }（外消旋-3 /内消旋-3）和外消旋/内消旋- PHP（3- t -Bu-C 5 H 3）2 } Zr PhN（CH 2）3 NPh}（rac -4 / meso -4）通过K 2 [PHP（3- t -Bu- C 5 H 3）2 ]·1.3 THF（2）和Zr RN（CH 2）3 NR} Cl 2（THF）2（其中R = SiMe 3或Ph分别），使用醚溶剂。这些同分异构对通过1 H，13 C 1 H}和31 P 1 H} NMR光谱进行表征。还通过单晶X射线晶体学检查了rac -3和rac -4。的结构外消旋-3和外消旋-4是在环戊二烯基环的朝向η的倾向显着3协调。分离的rac -3 / meso -3和rac -4 / meso -4样品在四氢呋喃-d
• Chelate-Controlled Synthesis of Racemic <i>a</i><i>nsa</i>-Zirconocenes
  作者：Matthew D. LoCoco、Xingwang Zhang、Richard F. Jordan

  DOI：10.1021/ja046629+

  日期：2004.11.1

  The reaction of ZrPhN(CH2)(3)NPh}Cl-2(THF)(2) (5) with lithium ansa-bis-indenyl reagents Li-2[XBI]-(Et2O) (XBI = (1-indenyl)(2)SiMe2 (SBI, 7a), (2-methyl-1-indenyl)(2)SiMe2 (MSBI, 7b), (2-methyl-4,5-benz-1-indenyl)(2)SiMe2 (MBSBI, 7c), (2-methyl-4-phenyl-1-indenyl)(2)SiMe2 (MPSBI, 7d), and 1,2-(1-indenyl)(2)ethane (EBI, 7e)) affords rac-(XBI)ZrPhN(CH2)(3)NPh} (8a-e) in high yield. The meso isomers were not detected by H-1 NMR. X-ray crystallographic studies show that the ZrPhN(CH2)(3)NPh) rings in 5, 8a, 8c, and (C5H5)(2)-ZrPhN(CH2)(3)NPh} (10) adopt twist conformations that position the N-Ph groups on opposite sides of the N-Zr-N plane. This conformation complements the metallocene structures of rac-8a-e but would destabilize the corresponding meso isomers. It is proposed that the ZrPhN(CH2)(3)NPh} ring adopts a similar twist conformation in the stereodetermining transition state for addition of the second indenyl ring in these reactions, which leads to a preference for rac products. The results of metallocene syntheses from other Zr amide precursors support this proposal. 8a-e are converted to the corresponding rac-(XBI)ZrCl2 complexes (9a-e) by reaction with HCl.
• Chelate-Controlled Synthesis of <i>rac-</i> and <i>meso-</i>Me₂Si(3-^tBu-C₅H₃)₂ZrCl₂
  作者：Matthew D. LoCoco、Richard F. Jordan

  DOI：10.1021/om034184c

  日期：2003.12.1

  The reaction of the chelated bis-amide complex ZrPhN(CH2)(3)NPh}Cl-2(THF)(2) (2) with Li-2[Me2Si(3-Bu-t-C5H3)(2)] yields meso-Me2Si(3-Bu-t-C5H3)(2)ZrPhN(CH2)(3)NPh} (meso-3) in > 98% yield. In contrast, the reaction of ZrMe3SiN(CH2)(3)NSiMe3}Cl-2(THF)(2) (4) or the related mono-THF adduct ZrMe3SiN(CH2)(3)NSiMe3}Cl-2(THF) (5) with Li-2[Me2Si(3-Bu-t-C5H3)(2)] yields rac-Me2Si(3-Bu-t-C5H3)(2)ZrMe3SiN(CH2)(3)NSiMe3} (rac-6) in quantitative NMR yield and 89% isolated yield. X-ray crystallographic analyses show that the ZrRN(CH2)(3)NR} chelate ring in rac-6 has a pronounced twist conformation, while that in meso-3 has a flatter, envelope conformation. It is proposed that the conformations of the ZrRN(CH2)(3)NR} chelate rings in the stereodetermining transition states for addition of the second Cp- ring in these reactions are similar to those in the metallocene products and control the diastereoselectivity. meso-3 and rac-6 are converted to meso-Me2Si(3-Bu-t-C5H3)(2)ZrCl2 (meso-1) and rac-1, respectively, by reaction with HCl in Et2O.