| 1228192-26-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• CAS: 1228192-26-4
• 化学式: C₂₃H₂₈NO₂PSi
• 分子量: 409.54
• InChiKey: OFCWNHQDKMEXNR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.05
• 重原子数：
  28.0
• 可旋转键数：
  8.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  42.35
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  、 (3-羧丙基)三甲基氯化铵 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 乙腈 为溶剂， 反应 20.0h， 以90%的产率得到
  参考文献：
  名称：

  Online Monitoring of Hydroformylation Intermediates by ESI-MS

  摘要：

  Self-assembling ligands bearing permanently charged moieties have been synthesized and investigated in the Rh-catalyzed hydroformylation of terminal alkenes. By coupling a high-pressure autoclave directly to an ESI mass spectrometer hydroformylation reactions applying self-assembling 6-DPPon ligands could be studied in an online fashion. The live-streaming of the reaction mixture to the spectrometer revealed a series of different complexes not observed by other methods before, the structures of which were corroborated by CID experiments. Under CO/H-2 atmosphere, new complexes that are predicted by the Wilkinson catalytic cycle could be identified and studied by CID experiments, too. Especially the ion at m/z 848, a square-planar hydrido-carbonyl complex that is normally not detectable by other methods, was investigated in detail. Collision experiments of this complex resulted in the loss of CO and H-2, the latter being quite unusual, and points to the involvement of the hydrogen bond framework. These findings were further supported by deuteration experiments that revealed a clear incorporation of deuterium into the ligands. From these findings a new hydrogen-activation mechanism was proposed. Furthermore, substrate-containing complexes could be generated too, though a huge excess of substrate was necessary. CID experiments either with D-2 or Ar yielded nearly identical spectra, hinting at a complex that might result either from a beta-hydride elimination or from intramolecular oxidative addition of one of the ligands.

  DOI：

  10.1021/om100131t
• 作为产物：
  描述：

  在 甲醇 作用下， 以 四氢呋喃 为溶剂， 以91%的产率得到
  参考文献：
  名称：

  Online Monitoring of Hydroformylation Intermediates by ESI-MS

  摘要：

  Self-assembling ligands bearing permanently charged moieties have been synthesized and investigated in the Rh-catalyzed hydroformylation of terminal alkenes. By coupling a high-pressure autoclave directly to an ESI mass spectrometer hydroformylation reactions applying self-assembling 6-DPPon ligands could be studied in an online fashion. The live-streaming of the reaction mixture to the spectrometer revealed a series of different complexes not observed by other methods before, the structures of which were corroborated by CID experiments. Under CO/H-2 atmosphere, new complexes that are predicted by the Wilkinson catalytic cycle could be identified and studied by CID experiments, too. Especially the ion at m/z 848, a square-planar hydrido-carbonyl complex that is normally not detectable by other methods, was investigated in detail. Collision experiments of this complex resulted in the loss of CO and H-2, the latter being quite unusual, and points to the involvement of the hydrogen bond framework. These findings were further supported by deuteration experiments that revealed a clear incorporation of deuterium into the ligands. From these findings a new hydrogen-activation mechanism was proposed. Furthermore, substrate-containing complexes could be generated too, though a huge excess of substrate was necessary. CID experiments either with D-2 or Ar yielded nearly identical spectra, hinting at a complex that might result either from a beta-hydride elimination or from intramolecular oxidative addition of one of the ligands.

  DOI：

  10.1021/om100131t