[1,2,4-(Me3C)3C5H2]2Ce(2,3,4,5-C6HF4) | 1031691-00-5

• 英文名称: [1,2,4-(Me3C)3C5H2]2Ce(2,3,4,5-C6HF4)
• CAS: 1031691-00-5
• 化学式: C₄₀H₅₉CeF₄
• 分子量: 756.022
• InChiKey: GSUXIOHMIQJRFO-UHFFFAOYSA-N

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

• 作为反应物：
  描述：

  [1,2,4-(Me3C)3C5H2]2Ce(2,3,4,5-C6HF4) 以 neat (no solvent, solid phase) 为溶剂， 以100%的产率得到[1,2,4-(Me3C)3C5H2]2Ce(2,3,4,6-C6HF4)
  参考文献：
  名称：

  Fluorine for Hydrogen Exchange in the Hydrofluorobenzene Derivatives C₆H_xF_(6-x), where x = 2, 3, 4 and 5 by Monomeric [1,2,4-(Me₃C)₃C₅H₂]₂CeH: The Solid State Isomerization of [1,2,4-(Me₃C)₃C₅H₂]₂Ce(2,3,4,5-C₆HF₄) to [1,2,4-(Me₃C)₃C₅H₂]₂Ce(2,3,4,6-C₆HF₄)

  摘要：

  The reaction between monomeric bis(1,2,4-tri-tert-butylcyclopentadienyl)cerium hydride, CP'2CeH, and several hydrofluorobenzene derivatives is described. The aryl derivatives that are the primary products, CP'Ce-2(C6H5-xFx) where x = 1,2,3,4, are thermally stable enough to be isolated in only two cases, since all of them decompose at different rates to CP'2CeF and a fluorobenzyne; the latter is trapped by either solvent when C6D6 is used or by a Cp'H ring when C6D12 is the solvent. The trapped products are identified by GC/MS analysis after hydrolysis. The aryl derivatives are generated cleanly by reaction of the metallacycle, Cp'((Me3C)(2)C5H2C(Me-2)CH2)Ce, with a hydrofluorobenzene, and the resulting arylcerium products, in each case, are identified by their H-1 and F-19 NMR spectra at 20 degrees C. The stereochemical principle that evolves from these studies is that the thermodynamic isomer is the one in which the CeC bond is flanked by two ortho-CF bonds. This orientation is suggested to arise from the negative charge that is localized on the ipso-carbon atom due to C-o(delta+)F-o(delta-) polarization. The preferred regioisomer is determined by thermodynamic rather than kinetic effects; this is illustrated by the quantitative, irreversible solid-state conversion at 25 degrees C over two months of CP'Ce-2(2,3,4,5-C6HF4) to CP'Ce-2(2,3,4,6-C6HF4), an isomerization that involves a CeC(ipso) for C(ortho)F site exchange.

  DOI：

  10.1021/ja800639f
• 作为产物：
  描述：

  bis(1,2,4-tri-tert-butylcyclopentadienyl)cerium benzyl 、 四氟苯 以 正戊烷 为溶剂， 以37%的产率得到[1,2,4-(Me3C)3C5H2]2Ce(2,3,4,5-C6HF4)
  参考文献：
  名称：

  Fluorine for Hydrogen Exchange in the Hydrofluorobenzene Derivatives C₆H_xF_(6-x), where x = 2, 3, 4 and 5 by Monomeric [1,2,4-(Me₃C)₃C₅H₂]₂CeH: The Solid State Isomerization of [1,2,4-(Me₃C)₃C₅H₂]₂Ce(2,3,4,5-C₆HF₄) to [1,2,4-(Me₃C)₃C₅H₂]₂Ce(2,3,4,6-C₆HF₄)

  摘要：

  The reaction between monomeric bis(1,2,4-tri-tert-butylcyclopentadienyl)cerium hydride, CP'2CeH, and several hydrofluorobenzene derivatives is described. The aryl derivatives that are the primary products, CP'Ce-2(C6H5-xFx) where x = 1,2,3,4, are thermally stable enough to be isolated in only two cases, since all of them decompose at different rates to CP'2CeF and a fluorobenzyne; the latter is trapped by either solvent when C6D6 is used or by a Cp'H ring when C6D12 is the solvent. The trapped products are identified by GC/MS analysis after hydrolysis. The aryl derivatives are generated cleanly by reaction of the metallacycle, Cp'((Me3C)(2)C5H2C(Me-2)CH2)Ce, with a hydrofluorobenzene, and the resulting arylcerium products, in each case, are identified by their H-1 and F-19 NMR spectra at 20 degrees C. The stereochemical principle that evolves from these studies is that the thermodynamic isomer is the one in which the CeC bond is flanked by two ortho-CF bonds. This orientation is suggested to arise from the negative charge that is localized on the ipso-carbon atom due to C-o(delta+)F-o(delta-) polarization. The preferred regioisomer is determined by thermodynamic rather than kinetic effects; this is illustrated by the quantitative, irreversible solid-state conversion at 25 degrees C over two months of CP'Ce-2(2,3,4,5-C6HF4) to CP'Ce-2(2,3,4,6-C6HF4), an isomerization that involves a CeC(ipso) for C(ortho)F site exchange.

  DOI：

  10.1021/ja800639f