diiodo(η5-cyclopentadienyl)(η5-3-trimethylsilyl-6,6-dimethylcyclohexadienyl)zirconium | 940909-92-2

• 英文名称: diiodo(η5-cyclopentadienyl)(η5-3-trimethylsilyl-6,6-dimethylcyclohexadienyl)zirconium
• CAS: 940909-92-2
• 化学式: C₁₆H₂₄I₂SiZr
• 分子量: 589.485
• InChiKey: DCXBGRUEUNIPNV-UHFFFAOYSA-L

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：

  π-cyclopentadienyl zirconium dichloride bromide 、 1,2-二碘乙烷 、 K(3-trimethylsilyl-6,6-dimethylcyclohexadienyl) 在 PMe₃ 作用下， 以 四氢呋喃 为溶剂， 以40%的产率得到diiodo(η5-cyclopentadienyl)(η5-3-trimethylsilyl-6,6-dimethylcyclohexadienyl)zirconium
  参考文献：
  名称：

  Silyl Substitution Effects on Metal−Pentadienyl Bonding:  Synthesis, Structure, Photoelectron Spectroscopy, and Electronic Structure of a High-Valent Half-Open Zirconocene

  摘要：

  The molecule Cp(3-Me3Si-6,6-dmch)ZrI2 (Cp = eta(5)-cyclopentadienyl; 3-Me3Si-6,6-dmch = eta(5)-3-trimethylsilyl-6,6-dimethylcyclohexadienyl) has been synthesized, and the molecular and electronic structures have been investigated. Photoelectron spectroscopy shows that substitution of a trimethylsilyl group in place of a hydrogen atom on the 6,6-dmch ligand destabilizes all of the ionizations of Cp(3-Me3Si-6,6-dmch)ZrI2 by ca. 0.1-0.2 eV compared to those of Cp(6,6-dmch)ZrI2. Density functional calculations accurately reproduce the experimental structure of the molecule and agree with the observed shift of all ionizations to lower energies. Interestingly, the ionizations are calculated to shift to lower energies without the expected increase in electron density at the metal center. This apparent contradiction is understood from analysis of one-center and two-center charge effects in the molecule. As a consequence of these charge effects, the silyl substitution makes the 3-Me3Si-6,6-dmch ligand a slightly better donor and, surprisingly, also a better acceptor ligand than the 6,6-dmch ligand.

  DOI：

  10.1021/om070008i