[(1,2,4-(Me3C)3C5H2)2Ce(OSO2CH3)] | 1357027-25-8

• 英文名称: [(1,2,4-(Me3C)3C5H2)2Ce(OSO2CH3)]
• CAS: 1357027-25-8；1357027-30-5
• 化学式: C₃₅H₆₁CeO₃S
• 分子量: 702.054
• InChiKey: DZWYILIHLLRILG-UHFFFAOYSA-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：

  甲磺酸甲酯 、 [(1,2,4-tri-tert-butylcyclopentadienyl)2Ce(OMe)] 以 氘代苯 为溶剂， 生成 [(1,2,4-(Me3C)3C5H2)2Ce(OSO2CH3)]
  参考文献：
  名称：

  Selectivity in the C–H Activation Reaction of CH₃OSO₂CH₃ with [1,2,4-(Me₃C)₃C₅H₂]₂CeH or [1,2,4-(Me₃C)₃C₅H₂][1,2-(Me₃C)₂-4-(Me₂CCH₂)C₅H₂]Ce: To Choose or Not To Choose

  摘要：

  The experimental reaction of [1,2,4-(Me3C)(3)CsH2](2)CeH, Cp'2CeH, and CH3OSO2CH3 begins by alpha-C-H activation of the SCH3 group, forming CP'(2) CeCH2SO2(OCH3), which evolves into CP'2CeOCH3 with elimination of CH2 (and presumably SO2). Prolonged heating of this mixture (days at 60 degrees C) forms Cp'2CeOSO2CH3 and CH3OCH3. The metallacycle [1,2,4-(Me3C)(3)C5H2][1,2-(Me3C)(2)-4-(Me2CCH2)C3H2)Ce, when presented with the choice of C-H bonds in CH3S and CH3O groups, deprotonates both with comparable rates, ultimately forming Cp'(2) CeOCH3 and Cp'2CeOSO2CH3 at 20 degrees C. The experimental studies are illuminated by DFT calculations on the experimental systems, which show that the hydride selects the more acidic CH3S bond, whereas the metallacycle reacts with C-H bonds of both the CH3S and CH3O groups of CH3OSO2CH3. In the metallacycle reaction, the initially formed regioisomers, Cp'2CeCH2SO2(OCH3) and Cp'2CeCH2OSO2CH3, rearrange to the observed products, Cp'2CeOCH3 and Cp'2CeOSO2CH3, respectively, Furthermore, C-H activation at the SCH3 group forms two isomers of Cp'2CeCH2SO2(OCH3) in the reaction of CH3OSO2CH3 with the metallacycle and only one in the reaction with the hydride. The lack of selectivity in the reactions of the metallacycle relative to the hydride is due to the metallacycle's greater thermodynamic advantage and lower energy barriers, which are linked to the higher bond energy of Ce-H relative to Ce-C in the metallacycle.

  DOI：

  10.1021/om200842t