dideuteriocarbene | 14863-68-4

• 分子结构分类: 有机化合物 - 碳氢化合物 - 饱和烃
• 英文名称: dideuteriocarbene
• 英文别名: Dideuterio-methylen；Methylen-d(2)
• CAS: 14863-68-4
• 化学式: CH₂
• 分子量: 16.011
• InChiKey: HZVOZRGWRWCICA-DICFDUPASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  1
• 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

• 作为反应物：
  描述：

  dideuteriocarbene 、 乙烯 生成 乙烯-1,1-D2
  参考文献：
  名称：

  Boehland, T.; Temps, F.; Wagner, H. Gg., Berichte der Bunsen-Gesellschaft, 1986, vol. 90, p. 468 - 475

  摘要：

  DOI：
• 作为产物：
  描述：

  重氮甲烷-D2 生成 dideuteriocarbene
  参考文献：
  名称：

  Photochemical Experiments in Rigid Media at Low Temperatures. II. The Reactions of Methylene, Cyclopentadienylene and Diphenylmethylene

  摘要：

  DOI：

  10.1021/ja01531a008

文献信息

• Transition state vibrational level thresholds for the dissociation of triplet ketene
  作者：Sang Kyu Kim、Edward R. Lovejoy、C. Bradley Moore

  DOI：10.1063/1.468631

  日期：1995.2.22

  Rate constants for the unimolecular dissociation of ketene (CH2CO) and deuterated ketene (CD2CO) have been measured at the threshold for the production of CH2 (X̃ 3B1) or CD2 (X̃ 3B1) and CO (X̃ 1Σ+) by photofragmentation in a cold jet. The rate constant increases in a stepwise manner as energy increases. This is in accord with the long-standing premise that the rate of a unimolecular reaction is controlled by flux through quantized transition-state thresholds at each energy level for vibrational motion orthogonal to the reaction coordinate. The first step in rate constant and/or photofragment excitation (PHOFEX) spectrum gives accurate values for the barrier to dissociation above the zero-point energy of the products, 1281±15 cm−1 for CH2CO and 1071±40 cm−1 for CD2CO. The measured rate constants are fit by Rice–Ramsperger–Kassel–Marcus (RRKM) theory. The vibrational frequencies at the transition state obtained from the fits are compared with ab initio results. Vibrational motions at the transition state orthogonal to the reaction coordinate are also revealed in CO product rotational distributions. Calculations using an impulsive model which includes vibrational motions at the transition state reproduce the experimental dependence of the PHOFEX spectra on the CO J state quite well. The small dependence of rate constant on jet temperature (4–30 K) indicates that the Ka quantum number for rotation about its symmetry axis is conserved in the energized ketene molecule.
• Photodissociation of methylacetylene at 193 nm
  作者：Kanekazu Seki、Hideo Okabe

  DOI：10.1021/j100187a031

  日期：1992.4

  The photolysis of methylacetylene (MA) at 193 nm was studied using Fourier transform infrared spectroscopy for product analysis. Main primary processes are CH3C2H + h-nu --> CH3C2 + H and CH3C2H + h-nu --> CH2 + C2H2 with a quantum yield of 0.7 +/- 0.1 and 0.11 +/- 0.01, respectively. Cl2 was used as H atom scavenger. The CD3C2H photolysis was used to confirm that acetylene-d1 formed is a primary product and is independent of reactant pressures. The H atom addition to the center carbon atom of CD3C2H produces CD3 + C2H2 with a yield of 0.10 +/- 0.01; C2H2 is reduced to almost zero above 5 Torr of MA. The remaining H atom addition to the end carbon would produce allene and propylene. The photolysis of CD3C2H and Cl2 mixtures produces only HCl and DCl is not found, indicating that H atoms are dissociated immediately from the triple-bonded carbon, although the C-D bond in CD3C2H is much weaker.