methylidenesilanylium | 64840-95-5

• 分子结构分类: 有机化合物 - 碳氢化合物衍生物
• 英文名称: methylidenesilanylium
• CAS: 64840-95-5
• 化学式: CH₃Si
• 分子量: 43.1203
• InChiKey: VJBAMVHOJSNOGN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.22
• 重原子数：
  2.0
• 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：

  二氢甲基甲硅烷基阳离子 以 gas 为溶剂， 生成 methylidenesilanylium 、 methylsilanyliumdiyl 、 、 alkaline earth salt of/the/ methylsulfuric acid 、 methane
  参考文献：
  名称：

  Unimolecular dissociation of methylsilylium and monochloromethylsilylium in the gas phase

  摘要：

  The mechanisms for the lowest energy barrier pathways for unimolecular dissociation of CH3SiH2+ and CH3-Si(Cl)H+ were examined in the gas phase by using Fourier transform mass spectrometry (FIMS). Collision-activated dissociation (CAD) by using sustained ''off-resonance'' irradiation (SORI) was used to determine the lowest energy pathways for dissociation. The lowest energy pathway for decomposition of CH3SiH2+ is dehydrogenation. The mechanism for this dehydrogenation process was investigated by studying the decomposition of CH3SiD2+. Unfortunately, isotopic scrambling by reversible 1,2-hydrogen migrations precede dehydrogenation. Hence, no mechanistic information is obtained from this isotopic labeling experiment. SORI-CAD of CH3SiD2+ yields dehydrogenation as H-2 (0.67) and HD (0.33) with no D2 loss. The lowest energy pathway for dissociation of CH3Si(Cl)H+ is elimination of HCl. In contrast to CH3SiD2+, CH3Si(CI)D+ does not undergo isotopic scrambling upon CAD. SORI-CAD of CH3Si(Cl)D+ yields exclusive elimination of HCl(1,2-elimination) to yield CH2SiD+. Hence, the lowest energy pathway for dissociation of CH3Si(Cl)H+ is 1,2-elimination of HCI. 1,1-Elimination of DCl from CH3Si(CI)D+ to yield CH3Si+ is 38 kcal/mol more favorable than the 1,2-elimination process. Consequently, there must be a prohibitive barrier for the energetically more favorable 1,1-elimination process.

  DOI：

  10.1021/j100151a014

文献信息

• Wlodek; Fox; Bohme, Journal of the American Chemical Society, 1991, vol. 113, # 12, p. 4461 - 4468
  作者：Wlodek、Fox、Bohme

  DOI：——

  日期：——
• Unimolecular dissociation of methylsilylium and monochloromethylsilylium in the gas phase
  作者：R. Bakhtiar、C. M. Holznagel、D. B. Jacobson

  DOI：10.1021/j100151a014

  日期：1993.12

  The mechanisms for the lowest energy barrier pathways for unimolecular dissociation of CH3SiH2+ and CH3-Si(Cl)H+ were examined in the gas phase by using Fourier transform mass spectrometry (FIMS). Collision-activated dissociation (CAD) by using sustained ''off-resonance'' irradiation (SORI) was used to determine the lowest energy pathways for dissociation. The lowest energy pathway for decomposition of CH3SiH2+ is dehydrogenation. The mechanism for this dehydrogenation process was investigated by studying the decomposition of CH3SiD2+. Unfortunately, isotopic scrambling by reversible 1,2-hydrogen migrations precede dehydrogenation. Hence, no mechanistic information is obtained from this isotopic labeling experiment. SORI-CAD of CH3SiD2+ yields dehydrogenation as H-2 (0.67) and HD (0.33) with no D2 loss. The lowest energy pathway for dissociation of CH3Si(Cl)H+ is elimination of HCl. In contrast to CH3SiD2+, CH3Si(CI)D+ does not undergo isotopic scrambling upon CAD. SORI-CAD of CH3Si(Cl)D+ yields exclusive elimination of HCl(1,2-elimination) to yield CH2SiD+. Hence, the lowest energy pathway for dissociation of CH3Si(Cl)H+ is 1,2-elimination of HCI. 1,1-Elimination of DCl from CH3Si(CI)D+ to yield CH3Si+ is 38 kcal/mol more favorable than the 1,2-elimination process. Consequently, there must be a prohibitive barrier for the energetically more favorable 1,1-elimination process.