monochlorosilylene | 13931-97-0

• 英文名称: monochlorosilylene
• 英文别名: chlorosilylene
• CAS: 13931-97-0
• 化学式: ClHSi
• 分子量: 64.5464
• InChiKey: DESGIDRJCLIWRS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.04
• 重原子数：
  2
• 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：

  monochlorosilylene 、 二氯硅烷 以 gaseous matrix 为溶剂， 生成 1,1,2-trichlorodisilane
  参考文献：
  名称：

  HSiCl与SiH 4和SiH 2 Cl 2的反应动力学

  摘要：

  HSiCl的激光激发荧光检测用于测量HSiCl与SiH 4和SiCl 2 H 2的反应的室温动力学。还获得了HSiCl + H 2速率系数的上限。将HSiCl插入SiH 4和SiCl 2 H 2的速率系数比将SiH 2插入Si-H键的速率系数小3-4个数量级。

  DOI：

  10.1016/0009-2614(86)80639-x
• 作为产物：
  描述：

  二氯硅烷 以 gaseous matrix 为溶剂， 生成 monochlorosilylene
  参考文献：
  名称：

  HSiCl与SiH 4和SiH 2 Cl 2的反应动力学

  摘要：

  HSiCl的激光激发荧光检测用于测量HSiCl与SiH 4和SiCl 2 H 2的反应的室温动力学。还获得了HSiCl + H 2速率系数的上限。将HSiCl插入SiH 4和SiCl 2 H 2的速率系数比将SiH 2插入Si-H键的速率系数小3-4个数量级。

  DOI：

  10.1016/0009-2614(86)80639-x

文献信息

• Direct detection of chlorosilylene and time resolved study of some of its reactions in the gas-phase using a new photochemical precursor
  作者：R. Becerra、S.E. Boganov、M.P. Egorov、I.V. Krylova、O.M. Nefedov、R. Walsh

  DOI：10.1016/j.cplett.2005.07.079

  日期：2005.9

  time at 457.9 nm using a CW argon ion laser. The kinetics of reactions of ClSiH with C2H4, CH2CHCMe3, C2H2, Me2O, SO2, HCl, MeSiH3, Me2SiH2, Me3SiH, MeGeH3, Me2GeH2 and precursor have been studied at ambient temperatures for the first time. Addition reactions of ClSiH and reactions with lone pair donors are faster than insertion reactions. Surprisingly ClSiH inserts faster into Si–H than Ge–H bonds

  通过在气相中通过1-nm-1-silacyclopent-3-ene的193 nm激光快速光解法制备亚甲叉基（ClSiH）。使用CW氩离子激光器在457.9 nm处实时监测ClSiH。ClSiH与C 2 H 4，CH 2 CHCMe 3，C 2 H 2，Me 2 O，SO 2，HCl，MeSiH 3，Me 2 SiH 2，Me 3 SiH，MeGeH 3，Me 2 GeH 2的反应动力学。首次在环境温度下对前驱体和前驱体进行了研究。ClSiH的加成反应和与孤对供体的反应比插入反应更快。出乎意料的是，ClSiH插入到Si–H中的速度比Ge–H键快。ClSiH在SiH 2和SiCl 2之间的反应性中间。ClSiH和SiH 2的相对反应性差异很大。
• Unusual Isotope Effect in the Reaction of Chlorosilylene with Trimethylsilane-<i>1</i>-<i>d</i>. Absolute Rate Studies and Quantum Chemical and Rice–Ramsperger–Kassel–Marcus Calculations Provide Strong Evidence for the Involvement of an Intermediate Complex
  作者：Rosa Becerra、Sergey E. Boganov、Mikhail P. Egorov、Irina V. Krylova、Vladimir M. Promyslov、Robin Walsh

  DOI：10.1021/ja301924b

  日期：2012.6.27

  [(13.20 ± 1.00) kJ mol(-1)]/(RT ln 10). When compared with previously published kinetic data for the reaction of ClSiH with Me(3)SiH, kinetic isotope effects, k(D)/k(H), in the range from 7.4 (297 K) to 6.4 (407 K) were obtained. These far exceed values of 0.4-0.5 estimated for a single-step insertion process. Quantum chemical calculations (G3MP2B3 level) confirm not only the involvement of an intermediate

  通过 1-chloro-1-silacyclopent-3-ene 的 193 nm 激光闪光光解产生的氯亚硅烷 (ClSiH) 的时间分辨研究已经进行，以获得其与三甲基硅烷-1-d、Me 的双分子反应的速率常数(3)SiD，气相。在 295-407 K 的温度范围内，在高达 100 Torr（添加和不添加 SF(6)）的总压力下研究反应。发现速率常数与压力无关，并给出以下 Arrhenius 方程：log[( k/(cm(3) 分子(-1) s(-1))] = (-13.22 ± 0.15) + [(13.20 ± 1.00) kJ mol(-1)]/(RT ln 10)。先前公布的 ClSiH 与 Me(3)SiH 反应的动力学数据，动力学同位素效应 k(D)/k(H)，范围从 7.4 (297 K) 到 6.4 (407 K)。这些远超过为单步插入过程估计的 0.4-0.5 的值。量子化学计算（G3MP2B3
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: S: MVol.B3, 138, page 1821 - 1823
  作者：

  DOI：——

  日期：——
• Besson, A.; Fournier, L., Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1909, vol. 148, p. 1192 - 1194
  作者：Besson, A.、Fournier, L.

  DOI：——

  日期：——
• Time-Resolved Gas-Phase Kinetic and Quantum Chemical Studies of Reactions of Silylene with Chlorine-Containing Species. 1. HCl
  作者：Rosa Becerra、J. Pat Cannady、Robin Walsh

  DOI：10.1021/jp037630i

  日期：2004.5.1

  Time-resolved kinetic studies of the reaction of silylene, SiH2, generated by laser flash photolysis of phenylsilane, have been carried out to obtain rate constants for its bimolecular reaction with HCL The reaction was studied in the gas phase at 10 Torr total pressure in SF6 bath gas, at five temperatures in the range of 296-611 K. The second-order rate constants fitted the Arrhenius equation: log(k/cm(3) molecule(-1) s(-1)) = (-11.51 +/- 0.06) + (1.92 +/- 0.47 kJ mol(-1))/RTIn10 Experiments at other pressures showed that these rate constants were unaffected by pressure in the range of 10-100 Torr, but showed small decreases in value of no more than 20% ( +/- 10%) at I Toff, at both the highest and lowest temperatures. The data are consistent with formation of an initial weakly bound donor-acceptor complex, which reacts by two parallel pathways. The first is by chlorine-to-silicon H-shift to make vibrationally excited chlorosilane, SiH3Cl*, which yields HSiCl by H-2 elimination from silicon. In the second pathway, the complex proceeds via H-2 elimination (4-center process) to make chlorosilylene, HSiCl, directly. This interpretation is supported by ab initio quantum calculations carried out at the G3 level which reveal the direct H-2 elimination route for the first time. RRKM modeling predicts the approximate magnitude of the pressure effect but is unable to determine the proportions of each pathway. The experimental data agree with the only previous measurements at room temperature. Comparisons with other reactions of SiH2 are also drawn.