2,2,2-trifluoroethylidene | 2441-28-3

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机氟化物
• 英文名称: 2,2,2-trifluoroethylidene
• 英文别名: trifluoromethylcarbene；2,2,2-trifluoro-ethane-1,1-diyl；trifluoromethyl-carbene；Trifluormethylcarben
• CAS: 2441-28-3
• 化学式: C₂HF₃
• 分子量: 82.0251
• InChiKey: BWXDTZVWCYJPCH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  5
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,2,2-trifluoroethylidene 反应 8.0h， 生成 顺式-1,1,1,4,4,4-六氟-2-丁烯 、 1,1,1,4,4,4-六氟-2-丁烯
  参考文献：
  名称：

  Matrix-Isolation and ab Initio Molecular Orbital Study of 2,2,2-Trifluoroethylidene

  摘要：

  Photolysis of 2,2,2-trifluorodiazoethane (2) in an argon matrix at 12 K generates tripler 2,2,2-trifluoroerhylidene (1) in addition to a significant amount of trifluoroethylene (3) and small amounts of trifluoromethyldiazirine (4). These compounds were identified by IR and UV spectroscopy. Short-wavelength photolysis of the carbene 1 converts it to trifluoroethylene, while slowly warming the matrix to 35 K results in dimerization to the isomeric hexafluorobut-2-enes. High-level ab initio calculations (QCISD(T)6-311(2D,2P)/MP2-FC/6-31G**) are reported for the singlet and triplet states of 2,2,2-trifluoroethylidene as well as for methylene and ethylidene. The calculated IR spectrum for triplet 2,2,2-trifluoroethylidene is in good agreement with the experimental one, but the UV/vis spectrum calculated using the CIS method does not match very well. The transition structures for the 1,2-fluorine atom rearrangement of the single and tripler states of carbene 1 to trifluoroethene were calculated at the QCISD(T)-FC/6-311(2D,2P)//MP2-FC/6-31G** level of theory. The calculated barrier for 1,2-fluorine atom migration in the singlet carbene, 21.5 kcal/mol, is less than suggested by recent experimental results (29 +/- 4 kcal/mol). The calculated barrier for the corresponding rearrangement in the triplet system was 51 kcal/mol. Previous reports concerning the energies and geometries of these calculated transition structures are shown to be in error.

  DOI：

  10.1021/ja00105a049
• 作为产物：
  描述：

  1,1,1,2-四氟乙烷 生成 2,2,2-trifluoroethylidene
  参考文献：
  名称：

  Buravtsev, N. N.; Grigor'ev, A. S.; Kolbanovskii, Yu. A., Russian Journal of Organic Chemistry, 1994, vol. 30, # 12, p. 1880 - 1890

  摘要：

  DOI：

文献信息

• Buravtsev, N. N.; Grigor'ev, A. S.; Kolbanovskii, Yu. A., Russian Journal of Organic Chemistry, 1994, vol. 30, # 12, p. 1880 - 1890
  作者：Buravtsev, N. N.、Grigor'ev, A. S.、Kolbanovskii, Yu. A.、Ovsyannikov, A. A.

  DOI：——

  日期：——
• Matrix-Isolation and ab Initio Molecular Orbital Study of 2,2,2-Trifluoroethylidene
  作者：John E. O'Gara、William P. Dailey

  DOI：10.1021/ja00105a049

  日期：1994.12

  Photolysis of 2,2,2-trifluorodiazoethane (2) in an argon matrix at 12 K generates tripler 2,2,2-trifluoroerhylidene (1) in addition to a significant amount of trifluoroethylene (3) and small amounts of trifluoromethyldiazirine (4). These compounds were identified by IR and UV spectroscopy. Short-wavelength photolysis of the carbene 1 converts it to trifluoroethylene, while slowly warming the matrix to 35 K results in dimerization to the isomeric hexafluorobut-2-enes. High-level ab initio calculations (QCISD(T)6-311(2D,2P)/MP2-FC/6-31G**) are reported for the singlet and triplet states of 2,2,2-trifluoroethylidene as well as for methylene and ethylidene. The calculated IR spectrum for triplet 2,2,2-trifluoroethylidene is in good agreement with the experimental one, but the UV/vis spectrum calculated using the CIS method does not match very well. The transition structures for the 1,2-fluorine atom rearrangement of the single and tripler states of carbene 1 to trifluoroethene were calculated at the QCISD(T)-FC/6-311(2D,2P)//MP2-FC/6-31G** level of theory. The calculated barrier for 1,2-fluorine atom migration in the singlet carbene, 21.5 kcal/mol, is less than suggested by recent experimental results (29 +/- 4 kcal/mol). The calculated barrier for the corresponding rearrangement in the triplet system was 51 kcal/mol. Previous reports concerning the energies and geometries of these calculated transition structures are shown to be in error.