bis{η-(1-cyclohexylethen-1-yl)cyclopentadienyl}zirconium dichloride | 135366-77-7

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: bis{η-(1-cyclohexylethen-1-yl)cyclopentadienyl}zirconium dichloride
• CAS: 135366-77-7
• 化学式: C₂₆H₃₄Cl₂Zr
• 分子量: 508.686
• InChiKey: QEHSTVSQAJWAEO-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  8.43
• 重原子数：
  29
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  bis{η-(1-cyclohexylethen-1-yl)cyclopentadienyl}zirconium dichloride 以 氘代苯 为溶剂， 以70%的产率得到
  参考文献：
  名称：

  双（烯基环戊二烯基）锆配合物的分子内光化学[2 + 2]环加成反应合成ansa-茂金属

  摘要：

  Reaction of the (alkenylcyclopentadienyl)lithium reagents [C5H4C(R)=CH2]Li (2a-c, R = cyclohexyl, phenyl, or o-tolyl) with ZrCl4(THF)2 gave the metallocene complexes [C5H4C(R)=CH2]2ZrCl2 (3a-c). Complex 3c was characterized by X-ray diffraction. It crystallizes in space group Cm with cell parameters a = 6.802(1) angstrom, b = 28.105(2) angstrom, c = 6.860(l) angstrom, beta = 114.5(1)-degrees, R = 0.023, and R(w) = 0.030. The reaction of the (1-alkenyl-3-alkylcyclopentadienyl)lithium reagents [(C5H3R1)C(R2)=CH2]Li (2d-f, R1 = isopropyl, R2 = phenyl or cyclohexyl and R1 = methyl, R2 = cyclohexyl) gave the metallocene complexes [(C5H3R1)C(R2)=CH2]2ZrCl2(3d-f). In each case a near to equimolar mixture of the respective rac and meso diastereoisomers was obtained. For 3d,e these were separated by fractional crystallization. rac-Bis[eta-1-(l-phenylethenyl)-3-isopropylcyclopentadienyl]zi rconium dichloride (rac-3d) was characterized by X-ray diffraction. It crystallizes in space group Pccn with cell parameters a = 22.122(l) angstrom, b = 15.594(l) angstrom, c = 16.576(1) angstrom, R = 0.045, and R(w) = 0.049. With the exception of 3c, these (alkenyl-CP)2ZrCI2 complexes 3 undergo rapid intramolecular [2 + 2] cycloaddition upon photolysis. The photostationary equilibrium reached is dependent on the substituent pattern of the starting materials and the wavelength of the light employed. Near to quantitative conversion to the novel cyclobutene-bridged ansa-metallocene complexes 11 is achieved when alkyl substituents are used and the irradiation is carried out at 450 nm. The photochemically induced coupling of readily introduced alkenyl functionalities represents a useful synthetic pathway to novel C2-hydrocarbyl-bridged ansa-metallocene systems of the early transition metals.

  DOI：

  10.1021/om00030a026
• 作为产物：
  描述：

  zirconium chloride-tetrahydrofuran 、 (1-cyclohexylethen-1-yl)cyclopentadienyllithium 以 四氢呋喃 、 甲苯 为溶剂， 以73%的产率得到bis{η-(1-cyclohexylethen-1-yl)cyclopentadienyl}zirconium dichloride
  参考文献：
  名称：

  Erker, Gerhard; Nolte, Rainer; Aul, Rainer, Journal of the American Chemical Society, 1991, vol. 113, # 20, p. 7594 - 7602

  摘要：

  DOI：

文献信息

• Erker, Gerhard; Nolte, Rainer; Aul, Rainer, Journal of the American Chemical Society, 1991, vol. 113, # 20, p. 7594 - 7602
  作者：Erker, Gerhard、Nolte, Rainer、Aul, Rainer、Wilker, Stephan、Krüger, Carl、Noe, Ralf

  DOI：——

  日期：——
• Synthesis of ansa-metallocenes by intramolecular photochemical [2 + 2] cycloaddition of bis(alkenylcyclopentadienyl)zirconium complexes
  作者：Gerhard Erker、Stephan Wilker、Carl Krueger、Matthias Nolte

  DOI：10.1021/om00030a026

  日期：1993.6

  Reaction of the (alkenylcyclopentadienyl)lithium reagents [C5H4C(R)=CH2]Li (2a-c, R = cyclohexyl, phenyl, or o-tolyl) with ZrCl4(THF)2 gave the metallocene complexes [C5H4C(R)=CH2]2ZrCl2 (3a-c). Complex 3c was characterized by X-ray diffraction. It crystallizes in space group Cm with cell parameters a = 6.802(1) angstrom, b = 28.105(2) angstrom, c = 6.860(l) angstrom, beta = 114.5(1)-degrees, R = 0.023, and R(w) = 0.030. The reaction of the (1-alkenyl-3-alkylcyclopentadienyl)lithium reagents [(C5H3R1)C(R2)=CH2]Li (2d-f, R1 = isopropyl, R2 = phenyl or cyclohexyl and R1 = methyl, R2 = cyclohexyl) gave the metallocene complexes [(C5H3R1)C(R2)=CH2]2ZrCl2(3d-f). In each case a near to equimolar mixture of the respective rac and meso diastereoisomers was obtained. For 3d,e these were separated by fractional crystallization. rac-Bis[eta-1-(l-phenylethenyl)-3-isopropylcyclopentadienyl]zi rconium dichloride (rac-3d) was characterized by X-ray diffraction. It crystallizes in space group Pccn with cell parameters a = 22.122(l) angstrom, b = 15.594(l) angstrom, c = 16.576(1) angstrom, R = 0.045, and R(w) = 0.049. With the exception of 3c, these (alkenyl-CP)2ZrCI2 complexes 3 undergo rapid intramolecular [2 + 2] cycloaddition upon photolysis. The photostationary equilibrium reached is dependent on the substituent pattern of the starting materials and the wavelength of the light employed. Near to quantitative conversion to the novel cyclobutene-bridged ansa-metallocene complexes 11 is achieved when alkyl substituents are used and the irradiation is carried out at 450 nm. The photochemically induced coupling of readily introduced alkenyl functionalities represents a useful synthetic pathway to novel C2-hydrocarbyl-bridged ansa-metallocene systems of the early transition metals.