Dichlormethylencarben | 20394-25-6

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 英文名称: Dichlormethylencarben
• 英文别名: 2,2-dichloro-ethene-1,1-diyl；dichloromethylene-carbene
• CAS: 20394-25-6
• 化学式: C₂Cl₂
• 分子量: 94.928
• InChiKey: VKMTZVKIFRDYMV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  4
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  三氯乙烯 以 gaseous matrix 为溶剂， 生成 二氯乙炔 、 Dichlormethylencarben 、 alkaline earth salt of/the/ methylsulfuric acid
  参考文献：
  名称：

  The mechanism of the unimolecular dissociation of trichloroethylene CHCl=CCl₂ in the ground electronic state

  摘要：

  The unimolecular dissociation of trichloroethylene in its electronic ground state has been investigated using an infrared multiphoton dissociation combined with photofragmentation translational spectroscopy to measure product translational energies. The main reaction channel was found to be HCl elimination on the basis of observed product time-of-flight (TOF) spectra. A center-of-mass translational energy distribution for this channel provides direct evidence for competition between two channels, three- and four-centered HCl eliminations. Cl elimination was found to be a minor but significant channel from observed Cl+ and C2HCl+TOF spectra. The branching ratios were determined as 0.28, 0.55, and 0.17 for the three- and four-centered HCl eliminations and the Cl elimination, respectively. The three-centered channel exhibits a ‘‘statistical’’ translational energy distribution which is typical for a reaction with no potential energy barrier in the reverse reaction, that is to say, no exit barrier reaction. In contrast, the four-centered channel exhibits a ‘‘nonstatistical’’ translational energy distribution having a peak at around 2 kcal/mol in energy, indicating that a significant exit barrier exists in the channel. The fraction of potential energy converted to translational energy was estimated to be around 10%. Ab initio calculations at the QCISD(T)/6-311+G**//MP2(FC)/6-31G* level were employed to confirm the reaction mechanism. The agreement in the energetics is quite good.

  DOI：

  10.1063/1.468989

文献信息

• The mechanism of the unimolecular dissociation of trichloroethylene CHCl=CCl₂ in the ground electronic state
  作者：Keiichi Yokoyama、Ginji Fujisawa、Atsushi Yokoyama

  DOI：10.1063/1.468989

  日期：1995.5.22

  The unimolecular dissociation of trichloroethylene in its electronic ground state has been investigated using an infrared multiphoton dissociation combined with photofragmentation translational spectroscopy to measure product translational energies. The main reaction channel was found to be HCl elimination on the basis of observed product time-of-flight (TOF) spectra. A center-of-mass translational energy distribution for this channel provides direct evidence for competition between two channels, three- and four-centered HCl eliminations. Cl elimination was found to be a minor but significant channel from observed Cl+ and C2HCl+TOF spectra. The branching ratios were determined as 0.28, 0.55, and 0.17 for the three- and four-centered HCl eliminations and the Cl elimination, respectively. The three-centered channel exhibits a ‘‘statistical’’ translational energy distribution which is typical for a reaction with no potential energy barrier in the reverse reaction, that is to say, no exit barrier reaction. In contrast, the four-centered channel exhibits a ‘‘nonstatistical’’ translational energy distribution having a peak at around 2 kcal/mol in energy, indicating that a significant exit barrier exists in the channel. The fraction of potential energy converted to translational energy was estimated to be around 10%. Ab initio calculations at the QCISD(T)/6-311+G**//MP2(FC)/6-31G* level were employed to confirm the reaction mechanism. The agreement in the energetics is quite good.