chloroformyl radical | 2602-42-8

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机氯化物
• 英文名称: chloroformyl radical
• 英文别名: Chlorcarbonyl-Radikal
• CAS: 2602-42-8
• 化学式: CClO
• 分子量: 63.4634
• InChiKey: DDKMFOUTRRODRE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  3
• 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：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  chloroformyl radical 生成 盐酸 、 一氧化碳
  参考文献：
  名称：

  The determination of the equilibrium and rate constants of the chain propagation and termination reactions in the photochemical formation of phosgene

  摘要：

  DOI：

  10.1039/tf9524800039
• 作为产物：
  描述：

  光气 在 一氧化碳 作用下， 以 gaseous matrix 为溶剂， 生成 chloroformyl radical
  参考文献：
  名称：

  Matrix‐Isolation Study of the Reaction of F Atoms with CO. Infrared and Ultraviolet Spectra of the Free Radical FCO

  摘要：

  FCO has been obtained in a CO and in an Ar matrix at 4°, 14°, and 20°K by the reaction with CO of F atoms produced upon photolysis of OF2, of NF2, or of t-N2F2, as well as by the photolysis of F2CO or of HFCO. The three vibrational fundamentals of the free radical FCO appear at 1855, 1018, and 626 cm−1. Experiments employing 13C16O and 12C18O confirm the infrared identification of FCO. In ultraviolet-absorption studies on matrix-isolated FCO an extensive series of bands has been observed between 2200 and 3400 Å. The most prominent progression in this system involves bands spaced at approximately 650-cm−1 intervals. It is likely that this progression is associated with the upper-state bending mode of FCO. F2CO and (FCO)2 are also produced in the reaction of F atoms with a CO matrix, and features of their infrared spectra are reported. A supplementary observation of the ultraviolet-absorption spectrum of gaseous F2CO shows a band system between 1800 and 2100 Å, with spacings of approximately 1700 cm−1. Presumably this system is contributed by the n→π* carbonyl transition. The approximate geometric structure and the nature of the chemical bonds of FCO are discussed, and the mechanisms of formation of this species and of the other observed products are considered. An estimate of the thermodynamic properties of FCO is given.

  DOI：

  10.1063/1.1696398

文献信息

• Gas-phase reactions between carbon monoxide, chlorine and nitrogen dioxide
  作者：J. H. Thomas、G. R. Woodman

  DOI：10.1039/tf9676302728

  日期：——

  The reactions between carbon monoxide, chlorine and nitrogen dioxide have been studied over the temperature range 381–473°C by manometric and photometric methods. The kinetic equations for this system has been established, and the proposed mechanism leads to a velocity constant for the reaction, COCl + NO2→CO2+NO + Cl of k= 108.84 exp (+160±250/RT)l. mole–1 sec–1.

  在381-473°C的温度范围内，通过压力计和光度计方法研究了一氧化碳、氯和二氧化氮之间的反应。建立了该体系的动力学方程，提出的机理导致反应COCl + NO2→CO2+NO + Cl的速度常数为k= 108.84 exp (+160±250/RT)升·摩尔–1·秒–1。
• Mechanism of Chlorine Catalytic Oxidation of CO in the Gas Phase
  作者：Tomohiro Ohta

  DOI：10.1246/bcsj.56.869

  日期：1983.3

  and/or ClO. The ratio of the competitive reactions of chloroformyl radicals, k8⁄k9a, was found to be (6.5±0.4)×10−2 in the total pressure range from 30 to 755 Torr (1 Torr=133 Pa); ClCO+Cl2→COCl2+Cl (8), ClCO+O2→ClC(O)O2* (9a). And also, the ratio of the competitive reactions of the vibrationally excited intermediates, k9b⁄k9c, was (3.4±0.3)×1018 molecule/cm3; ClC(O)O2*→ClCO+O2 (9b), ClC(O)O2*+M→ClC(O)O2+M

  标题反应的机理是在稳态条件下通过使用红外光谱在 300 K 下用黑蓝色荧光灯照射 Cl2、CO、O2 和 N2 的混合物来确定的。二氧化碳与光气 (COCl2) 形成速率之比的压力依赖性和其他结果表明，CO 的氧化是通过中间体 ClCO 和 ClC(O)O2 作为双分子过程进行的，而不是通过双分子氧化进行的。 ClOO和/或ClO。在30-755 Torr (1 Torr=133 Pa)的总压力范围内，氯甲酰基自由基的竞争反应比k8⁄k9a为(6.5±0.4)×10-2；ClCO+Cl2→COCl2+Cl (8), ClCO+O2→ClC(O)O2* (9a)。而且，振动激发的中间体k9b⁄k9c的竞争反应比为（3.4±0.3）×1018分子/cm3；ClC(O)O2*→ClCO+O2 (9b), ClC(O)O2*+M→ClC(O)O2+M (9c)。这种反应在平流层中的作用被讨论并估计不重要。
• Photochemical Reaction Channels of OCS with Cl₂, ICl, or IBr Isolated Together in an Argon Matrix:  Isolation of <i>syn</i>-Iodocarbonylsulfenyl Bromide
  作者：Yeny A. Tobón、Laura I. Nieto、Rosana M. Romano、Carlos O. Della Védova、Anthony J. Downs

  DOI：10.1021/jp056135e

  日期：2006.3.1

  Cl2 or ICl is the ClCO* radical which reacts subsequently with halogen or sulfur atoms or other matrix guests to give the corresponding carbonyl dihalide (OCCl2 and IC(O)Cl), syn-ClC(O)SCl or syn-ClC(O)SSCl. The analogous reaction with IBr affords syn-BrC(O)SBr, IC(O)Br, and syn-IC(O)SBr. The changes have been followed, the products characterized experimentally by IR measurements, and the spectra analyzed

  在X轴和Y轴的性质上，约15 K的Ar矩阵中一起分离出的二卤素XY（= Cl2，ICl或IBr）与OCS的光解诱导反应会导致产生不同的光产物。 ，OCCl2，syn-ClC（O）SCl，syn-ClC（O）SSCl，IC（O）Cl，IC（O）Br和syn-BrC（O）SBr，syn-碘羰基亚磺酰基溴，syn-IC（O）因此，SBr首次被鉴定为涉及IBr的反应的光产物。与Cl2或ICl反应形成的第一个产物是ClCO *基团，该基团随后与卤素或硫原子或其他基质客体反应，生成相应的羰基二卤化物（OCCl2和IC（O）Cl），syn-ClC（ O）SCl或syn-ClC（O）SSCl。与IBr的类似反应得到syn-BrC（O）SBr，IC（O）Br和syn-IC（O）SBr。进行了更改，
• Matrix Isolation FTIR Spectroscopic and Density Functional Theoretical Studies of the Nickel, Copper, and Silver Carbonyl Chlorides
  作者：Limin Shao、Luning Zhang、Mingfei Zhou、Qizong Qin

  DOI：10.1021/om000911h

  日期：2001.3.1

  The nickel, copper, and silver metal carbonyl chloride molecules have been prepared and isolated in solid argon by cocondensation of the species generated from 1064 nm laser ablation of metal chlorides with carbon monoxide in excess argon at 11 K. On the basis of isotopic substitution experiments and density functional theory frequency calculations, infrared absorptions at 2118.7, 2156.8, and 2184

  镍，铜和银的金属碳酰氯分子已经制备并通过在11 K下共冷凝1064 nm激光烧蚀金属氯化物与过量一氧化碳和过量的氩中产生的物质而在固体氩气中分离。根据密度函数理论频率计算，将2118.7、2156.8和2184.0 cm - 1处的红外吸收分配给Ni（CO）Cl，Cu（CO）Cl和Ag（CO）Cl分子的C-O拉伸振动。密度泛函计算预测M（CO）Cl（M = Ni，Cu，Ag）分子是线性的；相对于MC1 + CO的结合能估计分别为37.7、34.2和17.8kcal / mol。此外，还提供了有关M（CO）Cl 2，M（CO）的证据。2 Cl和M（CO）2 Cl 2（M = Ni，Cu）分子。
• FTIR spectroscopic study of 1,1,1-trifluoro-2-chloroethyl and 1,1,1-trifluoro-2-chloroethylperoxyl radicals
  作者：E.G. Baskir、V.A. Korolev、O.M. Nefedov

  DOI：10.1016/s0022-2860(98)00777-7

  日期：1999.5

  combination of matrix isolation and FTIR spectroscopy was applied to investigate 1,1,1-trifluoro-2-chloroethyl (1) and 1,1,1-trifluoro-2-chloroethylperoxyl (2) radicals. Radical 2 was obtained by vacuum pyrolysis of 1,1,1-trifluoro-2-bromo-2-chloroethane (3). Corresponding peroxyl radicals was generated by co-condensation of pyrolysis products and molecular oxygen in an argon matrix. To assign the

  摘要 结合基质分离和 FTIR 光谱来研究 1,1,1-三氟-2-氯乙基 (1) 和 1,1,1-三氟-2-氯乙基过氧 (2) 自由基。通过 1,1,1-三氟-2-溴-2-氯乙烷 (3) 的真空热解获得自由基 2。相应的过氧自由基是通过热解产物和分子氧在氩气基质中的共缩合产生的。为了分配实验波段，进行了 DFT 计算 (B3LYP/6–311G**)。过氧自由基 CF3CHClOO (1102.1, 972.7, cm-1) 的 O-O 和 C-O 伸缩振动的基带通过它们在 18O 取代衍生物的光谱中红移至 1044.7 和 954.1 cm-1 来识别。低温基质中自由基 2 的紫外光解产生二氟甲醛 CF2O、自由基 ClCO、CF3、