(PhNC(Me)CHC(Me)NPh)(η(5)-Cp)ZrCl2 | 203628-55-1

• 英文名称: (PhNC(Me)CHC(Me)NPh)(η(5)-Cp)ZrCl2
• 英文别名: (η5-C5H5)ZrCl2(CH(C(Me)(NC6H5))2)
• CAS: 203628-55-1
• 化学式: C₂₂H₂₂Cl₂N₂Zr
• 分子量: 476.56
• InChiKey: VXCMQRALHRHZTK-KTACSGBOSA-L

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：

  (PhNC(Me)CHC(Me)NPh)(η(5)-Cp)ZrCl2 、 甲基锂 以 乙醚 、 苯 为溶剂， 以60%的产率得到(PhNC(Me)CHC(Me)NPh)(η(5)-Cp)ZrMe2
  参考文献：
  名称：

  Synthesis and Structure of Acyclic Bis(ketenimine) Complexes of Zirconium

  摘要：

  Mono- and disubstituted bis(ketenimine) complexes of zirconium (1 and 2, respectively) can be readily prepared by reaction of these ligands (3) with Zr(NMe)(4) or, in some cases, the homoleptic tetrabenzyl derivative ZrBn4. Treatment of 1 (Ar = Ph, p-CF3Ph; X = NMe2) with Me2NH . HCl and of 2(Ar = Ph, X = NMe2) with either Me2NH . HCl or TMSCl provides the corresponding chloro derivatives in high yield. Alkyl derivatives of 2 (X = Me, Bn) can be readily prepared by reaction of the corresponding chloro derivatives with Grignard or organolithium reagents. Monocyclopentadienyl bis(ketenimine) complexes 4 (Ar Ph, p-CF3Ph; Cp = eta(5)-C5H5, eta(5)-C9H7; X = Cl) were prepared from 1 (Ar = Ph, p-CF3Ph; X = Cl) by reaction with CpLi or IndLi in high yield, and methyl derivatives 4 (Ar = Ph, p-CF,Ph; Cp = eta(5)-C5H5, eta(5)-C9H7; X = Me) were accessible by treatment of the chloro precursors with methyllithium. The X-ray structure of 2(Ar = Ph; X = NMe2) reveals a distorted-octahedral geometry in which the bis(ketenimine) ligands are sigma-bound to the metal and the dimethyl-amido groups are cis to one another, and the corresponding dichloro derivative also adopts a similar structure in the solid state, whereas the bis(ketenimine) ligands adopt a distorted, eta(5) binding mode in the monoindenyl derivative 4 (Ar = Ph; Cp = eta(5)-C9H7' X = Cl). Enantiomers of 2 (Ar = Ph, X = Cl) readily interconvert in solution via a Bailar-twist mechanism, as revealed by variable-temperature H-1 NMR spectroscopic studies; activation parameters for this process were determined (Delta H++ = 9.0 +/- 0.45 kcal mol(-1); Delta S++ = -9.9 +/- 1.0 cal mol(-1) K-1).

  DOI：

  10.1021/om970862h
• 作为产物：
  描述：

  、 sodium cyclopentadienide 以 苯 为溶剂， 以70%的产率得到(PhNC(Me)CHC(Me)NPh)(η(5)-Cp)ZrCl2
  参考文献：
  名称：

  Synthesis and Structure of Acyclic Bis(ketenimine) Complexes of Zirconium

  摘要：

  Mono- and disubstituted bis(ketenimine) complexes of zirconium (1 and 2, respectively) can be readily prepared by reaction of these ligands (3) with Zr(NMe)(4) or, in some cases, the homoleptic tetrabenzyl derivative ZrBn4. Treatment of 1 (Ar = Ph, p-CF3Ph; X = NMe2) with Me2NH . HCl and of 2(Ar = Ph, X = NMe2) with either Me2NH . HCl or TMSCl provides the corresponding chloro derivatives in high yield. Alkyl derivatives of 2 (X = Me, Bn) can be readily prepared by reaction of the corresponding chloro derivatives with Grignard or organolithium reagents. Monocyclopentadienyl bis(ketenimine) complexes 4 (Ar Ph, p-CF3Ph; Cp = eta(5)-C5H5, eta(5)-C9H7; X = Cl) were prepared from 1 (Ar = Ph, p-CF3Ph; X = Cl) by reaction with CpLi or IndLi in high yield, and methyl derivatives 4 (Ar = Ph, p-CF,Ph; Cp = eta(5)-C5H5, eta(5)-C9H7; X = Me) were accessible by treatment of the chloro precursors with methyllithium. The X-ray structure of 2(Ar = Ph; X = NMe2) reveals a distorted-octahedral geometry in which the bis(ketenimine) ligands are sigma-bound to the metal and the dimethyl-amido groups are cis to one another, and the corresponding dichloro derivative also adopts a similar structure in the solid state, whereas the bis(ketenimine) ligands adopt a distorted, eta(5) binding mode in the monoindenyl derivative 4 (Ar = Ph; Cp = eta(5)-C9H7' X = Cl). Enantiomers of 2 (Ar = Ph, X = Cl) readily interconvert in solution via a Bailar-twist mechanism, as revealed by variable-temperature H-1 NMR spectroscopic studies; activation parameters for this process were determined (Delta H++ = 9.0 +/- 0.45 kcal mol(-1); Delta S++ = -9.9 +/- 1.0 cal mol(-1) K-1).

  DOI：

  10.1021/om970862h

文献信息

• Dendritic β-diketiminato titanium and zirconium complexes: synthesis and ethylene polymerisation
  作者：Román Andrés、Ernesto de Jesús、F. Javier de la Mata、Juan C. Flores、Rafael Gómez

  DOI：10.1016/j.jorganchem.2004.10.041

  日期：2005.2

  The cyclopentadienyl(beta-diketiminato)titanium and zirconium chlorides (eta(5),C(5)H(5))MCl(2)(CH(C(NC(6)H(4)-4-OR)CH(3))(2)) (M = Ti (4-dend), Zr (5-dend)), where R corresponds to the first generation carbosilane dendron (dendritic wedge) Si(CH(2)CH(2)SiMePh(2))(3), have been synthesised. After activation with methylaluminoxane, the activity of 4-dend and 5-dend as catalysts for ethylene polymerisation has been determined and compared with that of the non-dedritic counterpart (eta(5)-C(5)H(5))MCl(2)CH(C(NC(6)H(5))CH(3))(2)) (M=Ti (4), Zr (5)). (C) 2004 Elsevier B.V. All rights reserved.