methylenebis(cyclopentadienyl)zirconium dichloride | 153052-32-5

• 英文名称: methylenebis(cyclopentadienyl)zirconium dichloride
• CAS: 153052-32-5
• 化学式: C₁₁H₁₀Cl₂Zr
• 分子量: 304.33
• InChiKey: MLGGPDULOZXOAD-UHFFFAOYSA-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：

  methylenebis(cyclopentadienyl)zirconium dichloride 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 生成 2-methyl-3-(8-quinolyl)cyclopent-2-enone
  参考文献：
  名称：

  [EN] SOLID-PHASE FLUORINATION OF BENZOTHIAZOLES
  [FR] FLUORATION EN PHASE SOLIDE DE BENZOTHIAZOLES

  摘要：

  公开号：

  WO2004056399A3
• 作为产物：
  描述：

  氯化锆(IV) 、 以 乙醚 为溶剂， 以17%的产率得到methylenebis(cyclopentadienyl)zirconium dichloride
  参考文献：
  名称：

  The Electronic Influence of Ring Substituents and Ansa Bridges in Zirconocene Complexes as Probed by Infrared Spectroscopic, Electrochemical, and Computational Studies

  摘要：

  The electronic influence of unbridged and ansa-bridged ring substituents on a zirconocene center has been studied by means of IR spectroscopic, electrochemical, and computational methods. With respect to IR spectroscopy, the average of the symmetric and asymmetric stretches upsilon(CO(av)) of a large series of dicarbonyl complexes (Cp-R)(2)Zr(CO)(2) has been used as a probe of the electronic influence of a cyclopentadienyl ring substituent. For unbridged substituents (Me, Et, Pr-,(i) Bu-t, SiMe3), upsilon(CO(av)) 1 on a per substituent basis correlates well with Hammett ameta parameters, thereby indicating that the influence of these substituents is via a simple inductive effect. In contrast, the reduction potentials (E) of the corresponding dichloride complexes (Cp-R)(2)ZrCl2 do not correlate well with Hammett sigma(meta) parameters, thereby suggesting that factors other than the substituent inductive effect also influence E. Ansa bridges with single-atom linkers, for example [Me2C] and [Me2Si], exert a net electron-withdrawing effect, but the effect is diminished upon increasing the length of the bridge. Indeed, with a linker comprising a three-carbon chain, the [CH2CH2CH2] ansa bridge becomes electron-donating. In contrast to the electron-withdrawing effect observed for a single [Me2Si] ansa bridge, a pair of vicinal [Me2Si] ansa bridges exerts an electron-donating effect relative to that from the single bridge. DFT calculations demonstrate that the electron-withdrawing effect of the [Me2C] and [Me2Si] ansa-bridges is due to stabilization of the cyclopentadienyl ligand acceptor orbital, which subsequently enhances back-donation from the metal. The calculations also indicate that the electron-donating effect of two vicinal [Me2Si] ansa bridges, relative to that of a single bridge, is a result of it enforcing a ligand conformation that reduces back-donation from the metal.

  DOI：

  10.1021/ja020236y