[(η5-C5H5)(η5-C5Me5)Zr[2,3,4,5-Ph4C4] | 1019335-60-4

• 英文名称: [(η5-C5H5)(η5-C5Me5)Zr[2,3,4,5-Ph4C4]
• CAS: 1019335-60-4
• 化学式: C₄₃H₄₀Zr
• 分子量: 648.015
• InChiKey: GMCKAPFEOJUPIQ-UHFFFAOYSA-N

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

• 作为产物：
  描述：

  (cyclopentadienyl)(pentamethylcyclopentadienyl)zirconium dichloride 、 二苯基乙炔 在 n-butyllithium 作用下， 以 四氢呋喃 为溶剂， 以60%的产率得到[(η5-C5H5)(η5-C5Me5)Zr[2,3,4,5-Ph4C4]
  参考文献：
  名称：

  Mechanism of Reversible Alkyne Coupling at Zirconocene:  Ancillary Ligand Effects

  摘要：

  The mechanism of reversible alkyne coupling at zirconium was investigated by examination of the kinetics of zinconacyclopentadiene cleavage to produce free alkynes. The zirconacyclopentadiene rings studied possess trimethylsilyl substituents in the a-positions, and the ancillary Cp-2, Me2C(eta(5)-C5H4)(2), and CpCp* (Cp* = eta(5)-C5Me5) bis(cyclopentadienyl) ligand sets were employed. Fragmentation of the zirconacyclopentadiene ring in Cp2Zr[2,5-(Me3Si)(2)-3,4-Ph2C4] with PMe3, to produce Cp2Zr(eta(5)-PhC CSiMe3)- (PMe3) and free PhC CSiMe3, is first-order in initial zirconacycle concentration and zero-order in incoming phosphine (k(obs) = 1.4(2) x 10(-5) s(-1) at 22 degrees C), and the activation parameters determined by an Eyring analysis (Delta H-double dagger = 28(2) kcal mol(-1) and Delta S-double dagger = 14(4) eu) are consistent with a dissociative mechanism. The analogous reaction of the ansa-bridged complex Me2C(eta(5)-C5H4)(2)Zr[2,5-(Me3Si)(2)-3,4-Ph2C4] is 100 times faster than that for the corresponding Cp-2 complex, while the corresponding CpCp* complex reacts 20 times slower than the Cp-2 derivative. These rates appear to be largely influenced by the steric properties of the ancillary ligands.

  DOI：

  10.1021/ja800025u