ethylenebis(cyclopentadienyl)zirconium dichloride | 122937-03-5

• 英文名称: ethylenebis(cyclopentadienyl)zirconium dichloride
• 英文别名: rac-Et(Ind)₂ZrCl₂
• CAS: 122937-03-5
• 化学式: C₁₂H₁₂Cl₂Zr
• 分子量: 318.357
• InChiKey: QCPATRXMYBYHAY-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：

  ethylenebis(cyclopentadienyl)zirconium dichloride 、 二异丁基氢化铝 以 氘代苯 为溶剂， 生成 H4C2(C5H4)2Zr(μ-H)3(Al(i-Bu)2)3(μ-Cl)2
  参考文献：
  名称：

  烷基铝配合的二茂锆氢化物：通过核磁共振光谱鉴定氢化物桥连物种

  摘要：

  未桥连的二氯化锆 (R(n)C(5)H(5-n))(2)ZrCl(2)（n = 0、1 或 2）与二异丁基氢化铝（HAl(i)Bu( 2)) 导致形成 (R(n)C(5)H(5-n))(2)Zr(mu-H)(3)(Al(i)Bu(2) 类型的四核三氢化物簇))(3)(mu-Cl)(2)，其中包含三个 [Al(i)Bu(2)] 单元。另一方面，发现了环桥联的 ansa-二氯化锆，Me(2)E(R(n)C(5)H(4-n))(2)ZrCl(2)，其中 E = C 或 Si形成 Me(2)E(R(n)C(5)H(4-n))(2)Zr(Cl)(mu-H)(2)Al(i)Bu( 2) 只有一个 [Al(i)Bu(2)] 单元。关于四核与双核产物形成的未桥接和桥接二茂锆衍生物之间的二分法被提议与它们的 C(5)-环配体的不同旋转自由度相关联。烷基铝络合的二氢化锆，

  DOI：

  10.1021/ja8054723
• 作为产物：
  描述：

  、 氯化锆(IV) 以 甲苯 为溶剂， 以21%的产率得到ethylenebis(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