(η5-Cp**o)2ZrCl2 | 156702-58-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (η5-Cp**o)2ZrCl2
• 英文别名: dichlorozirconium(2+);5-(2-methoxyethyl)cyclopenta-1,3-diene
• CAS: 156702-58-8
• 化学式: C₁₆H₂₂Cl₂O₂Zr
• 分子量: 408.479
• InChiKey: YLAYYZMXTVKXDL-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  -2.81
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (η5-Cp**o)2ZrCl2 、 silver trifluoromethanesulfonate 以 甲苯 为溶剂， 以70%的产率得到
  参考文献：
  名称：

  Titanocenes and zirconocenes with (chiral) O-functionalized side chains on the Cp ring

  摘要：

  A series of titanocene and zirconocene dichlorides was synthesized bearing ligands that contain a (chiral) ether group linked by an ethylene spacer group to the cyclopentadienyl ring. Surprisingly, the chiral zirconocenes (eta(5)-C5H4CH2CH2OR)(2)ZrCl2 with R = isobornyl and menthyl do not show Ziegler-Natta activity. This is probably caused by attack of the cocatalyst (MeAlO)(n) on the side chains, causing immobilization of the catalyst. Intramolecular coordination of the side chains is provoked by converting the dichlorides to the more Lewis-acidic mono and bis triflate complexes. The coordination of the ether chain depends on the size of the terminal group in the chain. In the achiral derivative (eta(5)-C5H4CH2CH2OMe)(2)Zr(O3SCF3)(2) there is a rapid equilibrium between species with one and two intramolecularly-coordinated ether side chains. The monotriflate complex (eta(5)-C(5)H(4)CH(2)CH(2)Oiso bornyl)(2)ZrCl(O3SCF3) decomposes rapidly, because ether coordination results in facile C-O bond cleavage and liberation of camphene. Accordingly, the bistriflate (eta(5)-C(5)H(4)CH(2)CH(2)Oisobornyl)(2)Zr(O3SCF3)(2) could not be synthesized. The chiral triflate complexes (eta(5)-C5H4CH2CH2OR)(2)Zr(O3SCF3)(2) with R = menthyl and fenchyl are active Diels-Alder catalysts, although no optical induction was observed, probably because the chiral ether handles are not sufficiently coordinated during catalysis. (C) 1998 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(97)00698-0
• 作为产物：
  描述：

  zirconium tetrachloride bis(tetrahydrofuran) complex 、 (2-Methoxyethyl)cyclopentadien 在 正丁基锂 作用下， 以 四氢呋喃 、 正戊烷 为溶剂， 以81%的产率得到(η5-Cp**o)2ZrCl2
  参考文献：
  名称：

  Titanocenes and zirconocenes with (chiral) O-functionalized side chains on the Cp ring

  摘要：

  A series of titanocene and zirconocene dichlorides was synthesized bearing ligands that contain a (chiral) ether group linked by an ethylene spacer group to the cyclopentadienyl ring. Surprisingly, the chiral zirconocenes (eta(5)-C5H4CH2CH2OR)(2)ZrCl2 with R = isobornyl and menthyl do not show Ziegler-Natta activity. This is probably caused by attack of the cocatalyst (MeAlO)(n) on the side chains, causing immobilization of the catalyst. Intramolecular coordination of the side chains is provoked by converting the dichlorides to the more Lewis-acidic mono and bis triflate complexes. The coordination of the ether chain depends on the size of the terminal group in the chain. In the achiral derivative (eta(5)-C5H4CH2CH2OMe)(2)Zr(O3SCF3)(2) there is a rapid equilibrium between species with one and two intramolecularly-coordinated ether side chains. The monotriflate complex (eta(5)-C(5)H(4)CH(2)CH(2)Oiso bornyl)(2)ZrCl(O3SCF3) decomposes rapidly, because ether coordination results in facile C-O bond cleavage and liberation of camphene. Accordingly, the bistriflate (eta(5)-C(5)H(4)CH(2)CH(2)Oisobornyl)(2)Zr(O3SCF3)(2) could not be synthesized. The chiral triflate complexes (eta(5)-C5H4CH2CH2OR)(2)Zr(O3SCF3)(2) with R = menthyl and fenchyl are active Diels-Alder catalysts, although no optical induction was observed, probably because the chiral ether handles are not sufficiently coordinated during catalysis. (C) 1998 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(97)00698-0

文献信息

• Monocyclopentadienyl and mono(2-methoxyethylcyclopentadienyl) zirconium methyl complexes
  作者：Chris Mattheis、Adolphus A.H van der Zeijden、Roland Fröhlich

  DOI：10.1016/s0022-328x(00)00117-0

  日期：2000.5

  The reactions of (eta(5)-Cp)ZrCl3(DME) and (eta(5):eta(1)-Cp-degrees)ZrCl3 (Cp degrees= C5H4CH2CH2OMe) with 1-2 equivalents of MeLi or MeMgI and THF yield the mono- and dimethyl zirconium complexes (eta(5)-Cp)ZrCl3-xMex(THF) and (eta(5):eta(1)-Cp degrees)ZrCl3-xMex (x = 1, 2), respectively. Reaction with three equivalents of MeMgI affords (eta(5)-Cp)ZrMe3(THF) and (eta(5):-eta(1)-Cp degrees)ZrMe3. The reaction with three equivalents of MeLi affords (eta(5)-Cp)(2)ZrMe2 or (eta(5)-Cp degrees)(2)ZrMe2 and ZrMe4, as a result of disproportionation. The reaction of (eta(5):eta(1)-Cp degrees)ZrMe3 with B(C6F5)(3) in THF affords the cationic zirconium complex [(eta(5):eta(1-)Cp degrees)ZrMe2(THF)][MeB(C6F5)(3)]. The chloride-bridged complex [(eta(5):eta(1)-Cp degrees)Zr(mu-Cl)Me-2](2) was characterized by single-crystal X-ray crystallography. (C) 2000 Elsevier Science S.A. All rights reserved.