(PhNC(Me)CHC(Me)NPh)(η(5)-Cp)ZrMe2 | 203628-58-4

• 英文名称: (PhNC(Me)CHC(Me)NPh)(η(5)-Cp)ZrMe2
• CAS: 203628-58-4
• 化学式: C₂₄H₂₈N₂Zr
• 分子量: 435.724
• InChiKey: XGSKQVYCPZNCPF-KTACSGBOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  (PhNC(Me)CHC(Me)NPh)(η(5)-Cp)ZrMe2 、 三苯碳四(五氟苯基)硼酸盐 以 further solvent(s) 为溶剂， 生成
  参考文献：
  名称：

  Ethylene Polymerization Using β-Diketimine Complexes of Zirconium

  摘要：

  Ethylene polymerizations were conducted using beta-diketimine complexes of Zr [LZrX3 (1) and L2ZrX2 (2) with L = MeC(NAr)CHC(NAr)Me and X = Cl, R (R = Me, Bn)] as well as Cp(L)ZrX2 (3) in the presence of MAO. Complexes 1 possess low polymerization activities (ca. 10(5) g PE/(mol Zr h)) and provide PEs with a trimodal, molecular weight distribution. Both 2 and 3 behave as single-site catalysts under these conditions, with the activity of the latter being considerably higher than the former (ca. 10(6)-10(7) vs 10(5) g PE/(mol Zr h)). Induction periods of 10-20 min at 70 degrees C were observed in polymerizations involving 3 (Ar = Ph, X = Cl, Me) when activated by MAO. The use of [Ph3C][B(C6F5)(4)] and 3b (Ar = Ph, X = Me) in the presence of small amounts of MAO (ca. 100:1 Al:Zr) led to rapid monomer uptake and an increase in catalytic activity by about a factor of 4. Lower activities were observed in the presence of Me3Al or (Bu3Al)-Bu-i. Little or no polymerization activity was observed when excess 3b was used as a scrubbing agent (in the presence of [Ph3C][B(C6F5)(4)]), and rapid loss of activity was observed when excess 3b was added to a catalyst system already producing PE. Complex 3b reacts with [Ph3C][B(C6F5)(4)] in chlorobenzene-d(5) solution at 25 degrees C to provide [Cp(L)ZrMe][B(C6F5)(4)] (4) Complex 4 is transformed on heating in chlorobenzene to a dicationic (mu-Cl)(2) complex [(Cp(L)ZrCl)(2)][B(C6F5)(4)](2) (5), which was characterized by X-ray crystallography. Complex 4 forms dinuclear complexes with 3b or Me3Al in solution at room temperature. These complexes, [Cp(L)Zr(mu-Me)(2)AlMe2][B(C6F5)(4)] (3) or [(Cp(L)ZrMe)(2)-(mu-Me)][B(C6F5)(4)] (7), are fluxional in solution; at lower temperature, the solution NMR spectra are consistent with the structures shown. Complex 3b is a potent inhibitor of ethylene polymerization by 4, forming 7, which is resistant to dissociation. The presence of AlMe3 (or MAO) appears to reversibly displace 3b from 7, allowing the reaction of 3b with [Ph3C][B(C6F5)(4)] to proceed to completion.

  DOI：

  10.1021/om9908027
• 作为产物：
  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