甲基-d2自由基 | 10457-12-2

• 中文名称: 甲基-d2自由基
• 英文名称: dideuteriomethyl
• CAS: 10457-12-2
• 化学式: CH₃
• 分子量: 17.0189
• InChiKey: WCYWZMWISLQXQU-DICFDUPASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.45
• 重原子数：
  1.0
• 可旋转键数：
  0.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  甲烷-d2 在 水 作用下， 生成 Monodeuteriomethyl 、 甲基-d2自由基
  参考文献：
  名称：

  Reaction on the O−+CH4 potential energy surface: Dependence on translational and internal energy and on isotopic composition, 93–1313 K

  摘要：

  Rate constants have been measured for the reactions of O− with CH4, CH2D2, and CD4 as a function of ion-neutral average center-of-mass kinetic energy, 〈KEcm〉, at several temperatures over the range 93 K–565 K using a selected ion flow drift tube apparatus. For the CH4 reaction we also report measurements made using a high-temperature flowing afterglow (HTFA) instrument over the temperature range 300 K–1313 K. The rate constants are found to have a very large isotope effect, with the CH4 rate constant a factor of 15 higher than the CD4 rate constant at 93 K. The rate constants generally have a minimum with respect to temperature and 〈KEcm〉, except for the higher-temperature data for CD4 where the rate constants show only an increase with increasing kinetic energy. The data indicate that increasing rotational temperature decreases the rate constants and that rotational energy behaves similarly to translational energy. Single excitations of bending and twisting vibrations have a negligible effect on the rate constant. Either the stretching vibrations or overtones of the bending vibrations increase the rate constants. If the stretches are responsible for the increase in the rate constants, the derived rate constant for a single quantum of stretch excitation (v=1) is 5×10−10 cm3 s−1, a factor of 6 larger than the rate constant for v=0. The CH2D2 rate constants are approximately equal to the averages of the rate constants for the pure isotopes. The product branching ratio (OH−/OD−) shows no dependence on CH2D2 rotational temperature or low-frequency CH2D2 vibrations. A theoretical study of the minimum energy reaction path was performed to help elucidate the reaction dynamics. The minimum energy reaction surface was characteristic of the standard double minimum pathway for ion molecule reactions. The height of the central barrier was found to be close to the energy of the reactants and varied with isotopic substitution. Conformationally different transition states are found for these isotopic reactions. Theoretical studies at the QCISD(T) level of theory find distinct transition states corresponding to O−+CH4, O−+H-CHD2, O−+D-CH2D, O−+CD4. The transition state barriers increase in the order O−+CH4, O−+H-CHD2, O−+D-CH2D, and O−+CD4, in agreement with experimental reaction rates. The main features of the reactivity are explained by the characteristics of the reaction surface.

  DOI：

  10.1063/1.473904

文献信息

• Isotope-Sensitive Degenerate [1,3]-Hydrogen Migration versus Competitive Enol-Keto Tautomerization
  作者：Xinhao Zhang、Waltraud Zummack、Detlef Schröder、Frank A. Weinhold、Helmut Schwarz

  DOI：10.1002/chem.200902176

  日期：2009.11.9

  acetone generated from its enol. Based on these findings as well as on highly accurate electronic structure calculations, a novel pathway (see picture) for a degenerate, isotope‐sensitive [1,3]‐hydrogen migration has been uncovered.

  非遍历行为：标记实验证实了由其烯醇生成的离子化丙酮的非遍历行为。基于这些发现以及高度精确的电子结构计算，已发现了一种简并的，对同位素敏感的[1,3]-氢迁移的新途径（见图）。
• Ion-molecule reactions in mixture of methane with water, hydrogen sulfide, and ammonia
  作者：Wesley T. Huntress、Russell F. Pinizzotto、James B. Laudenslager

  DOI：10.1021/ja00794a001

  日期：1973.6.27
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: S: SVol.4a/b, 1.3.8.11.1, page 212 - 214
  作者：

  DOI：——

  日期：——
• Schroeder, Detlef; Schwarz, Helmut, Angewandte Chemie, 1990, vol. 102, # 12, p. 1468 - 1469
  作者：Schroeder, Detlef、Schwarz, Helmut

  DOI：——

  日期：——
• Thermal decomposition of methanol in the sonolysis of methanol-water mixtures. Spin-trapping evidence for isotope exchange reactions
  作者：C. Murali. Krishna、Yves. Lion、Takashi. Kondo、Peter. Riesz

  DOI：10.1021/j100307a007

  日期：1987.11