1,1-bis(cyclopentadienyl)-1-zircona-2-oxa-6-methylcyclohexa-3,5-diene | 139167-72-9

• 英文名称: 1,1-bis(cyclopentadienyl)-1-zircona-2-oxa-6-methylcyclohexa-3,5-diene
• CAS: 139167-72-9
• 化学式: C₁₅H₁₆OZr
• 分子量: 303.515
• InChiKey: JKRIDGDMSNNQIJ-XHEODZGCSA-M

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

• 作为产物：
  描述：

  methyl(2-furyl)zirconocene 以 甲苯 为溶剂， 生成 1,1-bis(cyclopentadienyl)-1-zircona-2-oxa-6-methylcyclohexa-3,5-diene
  参考文献：
  名称：

  硫属元素金属环己二烯的热诱导呋喃基和噻吩锆茂新配合物的迁移环扩大

  摘要：

  Zirconocene dichloride reacts with 2 molar equiv of (2-furyl)lithium to give bis(2-furyl)zirconocene (1a). The (sigma-furyl)zirconocene complexes Cp2ZrR(2-furyl) (R = CH3, Ph, SiMe3) were similarly prepared by treatment of the respective Cp2Zr(R)Cl complexes with (2-furyl)lithium. Cp2Zr(SiMe3)(2-thienyl) was obtained from the reaction of Cp2Zr(SiMe3)Cl with (2-thienyl)lithium. The Cp2ZrR(2-furyl) complexes with R = 2-furyl, methyl, or phenyl all undergo an intramolecular high-temperature (greater-than-or-equal-to 180-degrees-C) sigma,sigma-exchange reaction to give the oxazirconacyclohexadienes Cp2 activated ZrOCH = CHCH = C(R) (2a-c). The 1a --> 2a rearrangement follows first-order kinetics in the temperature range 140-180-degrees-C and is characterized by the activation parameters DELTA-H double-ended-dagger = 30.9 +/- 2.0 kcal mol-1 and DELTA-S double-ended-dagger = -9 +/- 5 cal mol-1 K-1. The complexes Cp2Zr(SiMe3)(2-furyl) (1d) and Cp2Zr(SiMe3)(2-thienyl) (1e) undergo the analogous dyotropic rearrangements much faster. The 1d --> 2d isomerization is fast at 0-degrees-C and already takes place during the formation of 1d from Cp2Zr(SiMe3)Cl and (2-furyl)lithium. The activation parameters of the 1e --> 2e ring enlargement reaction of the (2-thienyl)metallocene system are DELTA-H double-ended-dagger = 20.4 +/- 2.0 kcal mol-1 and DELTA-S double-ended-dagger = -12 +/- 5 cal mol-1 K-1. The oxa- and thiazirconacyclohexadienes Cp2 activated Zr - X - CH = CHCH = C(SiMe3) (X = O, 2d; X = S, 2e) were characterized by X-ray diffraction. Complex 2d crystallizes in space group P1 with cell parameters a = 9.783 (1) angstrom, b = 11.514 (1) angstrom, c = 15.806 (1) angstrom, alpha = 96.27 (1)-degrees, beta = 101.64 (1)-degrees, gamma = 98.89 (1)-degrees, Z = 4, R = 0.037, and R(w) = 0.053. Complex 2e crystallizes in space group Cc with cell parameters a = 13.988 (4) angstrom, b = 30.774 (2) angstrom, c = 9.788 (4) angstrom, beta = 122.93 (1)-degrees, Z = 8, R = 0.034, and R(w) = 0.035. Both chalcogenazirconacyclohexadienes are monomeric in the solid state and exhibit nonplanar metallacyclic conformations with the metal-chalcogen vectors rotated significantly relative to the planes of the endocyclic conjugated diene moieties.

  DOI：

  10.1021/om00040a040