(C5H5)(CO)2Re(η(2)-MeHC=CMeO2CCF3) | 214900-54-6

• 英文名称: (C5H5)(CO)2Re(η(2)-MeHC=CMeO2CCF3)
• CAS: 214900-54-6
• 化学式: C₁₃H₁₂F₃O₄Re
• 分子量: 475.438
• InChiKey: OTCROWSHMYSJOO-PHSMJEINSA-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

• 作为产物：
  描述：

  Cp(CO)2Re(η2-MeCCMe) 、 三氟乙酸 以 氘代苯 为溶剂， 以85%的产率得到(C5H5)(CO)2Re(η(2)-MeHC=CMeO2CCF3)
  参考文献：
  名称：

  Acid-Catalyzed Isomerization of Rhenium Alkyne Complexes to Rhenium Allene Complexes via 1-Metallacyclopropene Intermediates

  摘要：

  The alkyne complexes C5Me5(CO)(2)Re(eta(2)-MeC=CMe) (1) and C5H5(CO)(2)Re(eta(2)-MeC=CMe) (6) underwent acid-catalyzed isomerization by way of 1-metallacyclopropene intermediates to form the allene complexes C5Me5(CO)(2)Re(eta(2)-2,3-MeHC=C=CH2) (5) and C5H5(CO)(2)Re(eta(2)-2,3-MeHC=C=CH2) (7). Stoichiometric reaction of 1 with CF3CO2H initially produced the kinetic addition product C5Me5(CO)(2)Re[eta(2)-(Z)-MeHC=CMeO2CCF3] (8-Z), which slowly isomerized to the thermodynamically more stable E isomer 8-E. The reaction of 6 with CF3CO2H at -73 degrees C produced only C5H5(CO)(2)Re[eta(2)-(E)-MeHC=CMeO2CCF3] (9-E), which isomerized at -60 degrees C to a 80:20 equilibrium mixture of 9-E and 9-Z. Treatment of 9-E and 9-Z with base led to formation of allene complex 7. The rate of this elimination was independent of base concentration. Labeling studies showed that the 1-metallacyclopropene intermediate C5H5(CO)(2)Re(eta(2)-CMeCHMe)+CF3CO2- (12-CF3CO2) undergoes a number of important reactions which include, in order of decreasing relative rates: (1) addition of trifluoroacetate to give enol trifluoroacetate complexes, (2) deprotonation to give complexed allenes, (3) degenerate 1,2-hydride migrations, (4) hydride migrations to give eta(3)-allyl complexes, and (5) deprotonation to give complexed alkynes.

  DOI：

  10.1021/om980348r