二氟卡宾(1+) | 54250-40-7

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 卤代烷
• 中文名称: 二氟卡宾(1+)
• 中文别名: 二氟卡宾(1+)
• 英文名称: difluoro carbene(1+)
• 英文别名: difluoromethyliumyl
• CAS: 54250-40-7
• 化学式: CF₂
• 分子量: 50.0078
• InChiKey: GABNKAYPQUNMGY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.92
• 重原子数：
  3.0
• 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

• 作为反应物：
  描述：

  二氟卡宾(1+) 在 氧化亚氮 作用下， 26.9 ℃ 、53.33 Pa 条件下， 生成 二氟卡宾 、 alkaline earth salt of/the/ methylsulfuric acid
  参考文献：
  名称：

  Chemistry of CFn+ (n = 1-3) ions with halocarbons

  摘要：

  The gas-phase reactions of CF+, CF2+, and CF3+ with the halocarbons CF3Cl, CF3Br, CF3I, CF4, and C2F6 have been studied using a variable-temperature-selected ion flow tube (VT-SIFT) instrument at 300 and 496 K. The ion CF+ reacts rapidly with CF3X (X = Cl, Br, I) producing the ions CF2X+. In the reaction of CF+ with CF3Cl, CF3+ is also produced as a minor product. Curvature was observed in the pseudo-first-order kinetics plots for the reactions of CF+ with CF4 and C2F6. In both cases the curvature is attributed to the presence of two or more CF+ states (probably vibrational) of differing reactivities toward the perfluorocarbon of interest. This conclusion is supported by our observation of charge transfer from CF+ to NO, a reaction which is endothermic by 15 kJ/mol for the ground state of CF+. CF+ is unreactive with O2, N2, and Xe. The reactions of CF2+ with CF3X yield CF3+ and CF2X+ for X = Cl and Br; for X = I, CF2I+ and CF3I+ are produced. The overall reactions proceed at approximately the collision rate at 300 and 496 K, and the branching ratios are not strongly dependent on temperature. The reactions of CF2+ with CF4 and C2F6 produce CF3+ and C2F5+, respectively. The rate constants decrease significantly with increasing temperature. CF2+ reacts rapidly by charge transfer with NO. The reaction of CF2+ with O2, producing CF2O+, is inefficient. CF2+ is unreactive with N2. CF3+ reacts with CF3X (X = Cl, Br, I) at rates below the collision values, producing a single ionic product, CF2X+. While the rate constants for the reactions of CF3+ with CF3X increase in the series with increasing CF3X mass, the rate constants for reaction with each CF3X decrease sharply with increasing temperature. A mechanism is proposed in which the reaction proceeds on a double-well potential energy surface. No reaction was observed for the CF3+/CF4 system. CF3+ appeared to react very slowly with C2F6 and NO, producing C2F5+ and NO+, respectively, but reactions with impurities in the neutral reagents cannot be ruled out as the source of these ions. CF3+ is unreactive with O2 and N2.

  DOI：

  10.1021/j100185a038
• 作为产物：
  描述：

  四氟化碳 以 neat (no solvent) 为溶剂， 生成 二氟卡宾(1+)
  参考文献：
  名称：

  Pfeifer, J.-P., Ber. Kernforsch. Anlage Juelich Nr. 651 (1970) 1/12

  摘要：

  DOI：

文献信息

• Study of the Gas Phase Reactions of Several Perfluorocarbons with Positive Ions of Atmospheric Interest
  作者：Gary K. Jarvis、Chris A. Mayhew、Richard P. Tuckett

  DOI：10.1021/jp960071d

  日期：1996.1.1

  studied that reacts with H3O+ at a measurable rate. All the other reactions take place at or close to the collisional rate, the exceptions being the reactions of N2O+ with C2F4 and C3F8, and CO2+ with C2F4 and C2F6, for which the experimental rate coefficients show marked departures from the collisional values. It is proposed that most of the reactions proceed through a complex intermediate resulting

  H 3 O +，NO +，O 2 +，H 2 O +，N 2 O +，O +，CO 2 +，CO +，N +和N 2 +反应的双分子速率系数和离子产物具有三个氟代烯烃（C 2 F 4，C 3 F 6和2-C 4 F 8）和三个完全饱和的全氟化碳（C 2 F 6，C 3 F报道了在300K下的8和n -C 4 F 10）。发现所有六个全氟化碳均与NO +不反应。C 2 F 6也与O 2 +，H 2 O +和N 2 O +不反应，并且C 3 F 8和n -C 4 F 10也与O 2 +不反应。C 3 F 6是唯一与H 3 O +反应的全氟化碳以可测量的速度 所有其他反应均以碰撞速度或接近碰撞速度的方式发生，但N 2 O +与C 2 F 4和C 3 F 8以及CO 2 +与C 2 F 4和C 2 F 6的反应除外。，其实验速率系数显示出与碰撞值的明显偏离。建议大多数反应通过复杂的中间体进行，导致
• Electron-stimulated chemistry of CF₃I adsorbed on Ag(111) C—F bond cleavage and C—C coupling
  作者：Jeffrey E. Fieberg、Andras Szabo、J. M. White

  DOI：10.1039/ft9969204739

  日期：——

  For CF3I adsorbed on Ag(111), reactions stimulated by 100 eV electrons are characterized by temperature programmed desorption (TPD) and reflection–absorption infrared spectroscopy (RAIRS). In the absence of electron irradiation, multilayers desorb at 100 K, two orientations in the first layer desorb at 110 and 128 K, and CF3 radical desorption occurs at 300 K. After electron irradiation of coverages below one layer [θ < 0.30 monolayer (ML)], the remaining parent desorption is broadly distributed between 110 and 225 K, there is a C2F5 radical desorption peak at 340 K and the 300 K CF3 radical desorption is replaced by a peak at 240 K. At coverages greater than 0.30 ML, TPD after electron irradiation reveals two new products (CF2I2 and C2F3I) formed in roughly equal amounts. RAIRS suggests that adsorbed CF2I2 has C2v symmetry with both I atoms bound to Ag. We propose that C—C coupling to form C2F5 occurs by insertion of CF2+ or CF2, formed by impact ionization of the parent, into adsorbed CF3, previously formed during either adsorption or the earlier stages of electron irradiation. CF2I2 formation is described in terms of two possible processes: (i) formation of I–, which reacts with neighbouring CF3I, and (ii) C—F fragmentation of CF3I+, formed in multilayers, into CF2I+, which reacts with previously formed atomic iodine. At 0.75 ML, the cross-section for loss of CF3I by all removal processes is 1.1 ± 0.2 × 10–16 cm2, whereas that for CF2I2 formation is ca. 10–17 cm2.

  对于吸附在 Ag(111) 上的 CF3I，100 eV 电子激发的反应是通过温度编程解吸（TPD）和反射吸收红外光谱（RAIRS）来描述的。在没有电子辐照的情况下，多层在 100 K 时解吸，第一层的两个取向在 110 K 和 128 K 时解吸，CF3 自由基在 300 K 时解吸。当覆盖层大于 0.30 ML 时，电子辐照后的 TPD 显示有两种新产物（CF2I2 和 C2F3I）形成，数量大致相同。RAIRS 表明，吸附的 CF2I2 具有 C2v 对称性，两个 I 原子都与 Ag 结合。我们认为，CâC 耦合形成 C2F5 是通过将母体撞击电离形成的 CF2+ 或 CF2 插入到吸附的 中发生的， 之前是在吸附或电子辐照的早期阶段形成的。CF2I2 的形成有两种可能的过程：(i) Iâ 的形成，它与邻近的 发生反应；(ii) 在多层中形成的 + 的 CâF 断裂成 CF2I+，它与之前形成的原子碘发生反应。在 0.75 ML 条件下，通过所有去除过程损失 的横截面为 1.1 ± 0.2 à 10â16 cm2，而形成 CF2I2 的横截面约为 10â17 cm2。
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: C: MVol.D2, 4.1.1.7.5, page 135 - 136
  作者：

  DOI：——

  日期：——
• McAskill, N. A., 1970, vol. 23, p. 893 - 903
  作者：McAskill, N. A.

  DOI：——

  日期：——
• Studies in electron impact methods. Part 2.—The latent heat of sublimation of carbon
  作者：Rowland I. Reed、Walter Snedden

  DOI：10.1039/tf9585400301

  日期：——