silylsilylene

• 分子结构分类: 无机化合物 - 混合金属/非金属化合物 - 各种混合金属/非金属
• 英文名称: silylsilylene
• 化学式: H₄Si₂
• 分子量: 60.2028
• InChiKey: BAGSMSWGHZVCIQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.83
• 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：

  乙硅烷 、 silylsilylene 以 gaseous matrix 为溶剂， 生成 正四硅烷
  参考文献：
  名称：

  Role of silylene in the deposition of hydrogenated amorphous silicon

  摘要：

  The role of silylene in the laser deposition of hydrogenated amorphous silicon has been studied with laser-induced fluorescence and deposition rate measurements. The rate constants of the reactions of silylene with silane and disilane and of the reverse reactions have been determined. The results show that silylene is rapidly consumed, exhibiting only a small effective lifetime. It proves that generally silylene will hardly be able to reach the surface to form amorphous silicon. The comparison of the kinetic data with the deposition rates shows that in IR laser CVD silylene starts the gas-phase chemistry and that disilene is the main film-forming molecule. The UV laser process starts with a different primary dissociation leading to silylsilylene, which also rearranges to the film-forming disilene.

  DOI：

  10.1021/j100176a050
• 作为产物：
  描述：

  二硅烯 生成 silylsilylene
  参考文献：
  名称：

  丁基和戊基亚甲硅烷基的分解动力学和热化学

  摘要：

  Reaction kinetics of alkylsilylenes (R = butyl, pentyl, and methylpentyl) and silacyclopropane intermediates produced by silylene additions to 1-butene, 1- and 2-pentene, 2-methyl-1-pentene, and 4-methyl-1-pentene are reported. Observations are consistent with a homogeneous, Barton2-type mechanism, which describes alkylsilylene isomerization and decomposition in terms of silacyclopropane (SCP) intermediates. Modeling studies on this basis conclude that SCP-forming and -opening reactions are at least an order of magnitude faster than SCP decompositions to olefins and SiH2. All reactions are pressure dependent at 400 Torr. Decomposition versus trapping comparative rate data at 410 Torr, based on butylsilylene- and pentylsilylene-trapping reactions with silane of 4.8 x 10(9) M-1 s-1 and 3.1 x 10(9) M-1 s-1, respectively, give limiting high-pressure Arrhenius parameters for the butyl- and pentylsilylene decompositions of log A infinity = 15.5 +/- 0.1, E infinity = 22.5 +/- 0.3 kcal. The activation energies are consistent with the decomposition reaction thermochemistries (DELTA-H(dec) = 26.6 +/- 3.4 kcal, DELTA-E(dec) = 25.3 +/- 3.4 kcal), and A factors indicate surprisingly loose transition states for both alkysilylene decompositions as well as their reverse silylene/olefin additions. A loose silylene/olefin addition complex is suggested for the transition state as the thermochemistry of decomposition precludes the intermediacy of biradicals. Generic high-pressure Arrhenius parameters (A, s-1: E, kcal) are deduced for silacyclopropane ring-opening (o), -closing (c), and -decomposition (d) reactions: log A(c) = 12.3, E(c) = 10.4; log A(o) = 14.0, E(o) = 14.7 + DELTA-E; log A(d) = 16.9, E(d) = 26.1 + DELTA-E, where DELTA-E = (49.6 - SCP strain energy). The low SCP ring-closing activation energy indicates zero ring strain development in the transition state and is consistent with a reanalysis of prior estimates of the activation energy of the SiH2 + CH4 strain free, C-H bond insertion reaction.

  DOI：

  10.1021/om00056a021

文献信息

• Role of silylene in the deposition of hydrogenated amorphous silicon
  作者：Thomas R. Dietrich、Stefano Chiussi、Michael Marek、Angelika Roth、Franz J. Comes

  DOI：10.1021/j100176a050

  日期：1991.11

  The role of silylene in the laser deposition of hydrogenated amorphous silicon has been studied with laser-induced fluorescence and deposition rate measurements. The rate constants of the reactions of silylene with silane and disilane and of the reverse reactions have been determined. The results show that silylene is rapidly consumed, exhibiting only a small effective lifetime. It proves that generally silylene will hardly be able to reach the surface to form amorphous silicon. The comparison of the kinetic data with the deposition rates shows that in IR laser CVD silylene starts the gas-phase chemistry and that disilene is the main film-forming molecule. The UV laser process starts with a different primary dissociation leading to silylsilylene, which also rearranges to the film-forming disilene.
• Decomposition kinetics and thermochemistry of butyl- and pentylsilylenes
  作者：A. P. Dickinson、H. E. O'Neal、M. A. Ring

  DOI：10.1021/om00056a021

  日期：1991.10

  Reaction kinetics of alkylsilylenes (R = butyl, pentyl, and methylpentyl) and silacyclopropane intermediates produced by silylene additions to 1-butene, 1- and 2-pentene, 2-methyl-1-pentene, and 4-methyl-1-pentene are reported. Observations are consistent with a homogeneous, Barton2-type mechanism, which describes alkylsilylene isomerization and decomposition in terms of silacyclopropane (SCP) intermediates. Modeling studies on this basis conclude that SCP-forming and -opening reactions are at least an order of magnitude faster than SCP decompositions to olefins and SiH2. All reactions are pressure dependent at 400 Torr. Decomposition versus trapping comparative rate data at 410 Torr, based on butylsilylene- and pentylsilylene-trapping reactions with silane of 4.8 x 10(9) M-1 s-1 and 3.1 x 10(9) M-1 s-1, respectively, give limiting high-pressure Arrhenius parameters for the butyl- and pentylsilylene decompositions of log A infinity = 15.5 +/- 0.1, E infinity = 22.5 +/- 0.3 kcal. The activation energies are consistent with the decomposition reaction thermochemistries (DELTA-H(dec) = 26.6 +/- 3.4 kcal, DELTA-E(dec) = 25.3 +/- 3.4 kcal), and A factors indicate surprisingly loose transition states for both alkysilylene decompositions as well as their reverse silylene/olefin additions. A loose silylene/olefin addition complex is suggested for the transition state as the thermochemistry of decomposition precludes the intermediacy of biradicals. Generic high-pressure Arrhenius parameters (A, s-1: E, kcal) are deduced for silacyclopropane ring-opening (o), -closing (c), and -decomposition (d) reactions: log A(c) = 12.3, E(c) = 10.4; log A(o) = 14.0, E(o) = 14.7 + DELTA-E; log A(d) = 16.9, E(d) = 26.1 + DELTA-E, where DELTA-E = (49.6 - SCP strain energy). The low SCP ring-closing activation energy indicates zero ring strain development in the transition state and is consistent with a reanalysis of prior estimates of the activation energy of the SiH2 + CH4 strain free, C-H bond insertion reaction.