[6,6]-(1-N-triphenylsilylmethyl-fulleroaziridine)-C60 | 1144111-39-6

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: [6,6]-(1-N-triphenylsilylmethyl-fulleroaziridine)-C60
• CAS: 1144111-39-6
• 化学式: C₇₉H₁₇NSi
• 分子量: 1008.1
• InChiKey: QENAVLYFYJAJMT-RTCKWZGYSA-N

物化性质

• 密度：
  2.35±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.23
• 重原子数：
  81.0
• 可旋转键数：
  5.0
• 环数：
  36.0
• sp3杂化的碳原子比例：
  0.04
• 拓扑面积：
  3.01
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  [6,6]-(1-N-triphenylsilylmethyl-triazoline)-C60 以 邻二氯苯 为溶剂， 反应 24.0h， 以33%的产率得到[6,6]-(1-N-triphenylsilylmethyl-fulleroaziridine)-C60
  参考文献：
  名称：

  Syntheses and crystal structures of azafulleroid and aziridinofullerene bearing silyl or germyl benzene

  摘要：

  Addition of silyl and germylmethyl azides (1) to fullerene C-60 at 50 degrees C through [2+3] cycloaddition led to the formation of the triazoline adducts (2). Subsequently, heating 2 at 100 degrees C in the solid state, caused N-2 extrusion producing two different isomers, [5,6]-azafulleroid (3) and [6,6]-aziridinofullerene (4). The C-13 NMR spectrum of 3 had an absence of resonances in the aliphatic region for the fullerene C-60 cage, showing a fulleroid with CS symmetry. In contrast, 4 exhibited one sp(3) resonance in the aliphatic region for the fullerene C-60 cage, indicative of an aziridinofullerene with C-2V symmetry. However, MALDI-TOF mass characterization was hampered because ion peaks corresponding to the bis-adduct are detected in positive ion mode measurements, whereas the ion peaks [M-N-2] for 2a as well as [M] for 3a and 4a are observed in negative ion measurements. In an effort to obtain X-ray data, silyl and germylphenyl groups were introduced to form intermolecular complexes with fullerene C-60. The X-ray structures of 3c and 3d revealed a strong enhancement of homoconjugation in the bridged annulene moiety based on POAV analysis. The X-ray structures of 3c,d and 4c were confirmed with the detection of silyl and germylphenyl-C-60 interactions, similar to dimethoxyphenyl-C-60 interactions. (C) 2008 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2008.11.049

文献信息

• Production of a 15-membered Ring Orifice in Open-cage Fullerenes by Double Photooxygenation of Azafulleroid
  作者：Houjin Hachiya、Yoshio Kabe

  DOI：10.1246/cl.2009.372

  日期：2009.4.5

  Photooxygenation of silyl-modified azafulleroids 1b and 1c gave open-cage fullerenes having keto lactam 2b and 2c or diketo imide 3b and 3c functional groups on 11- or 15-membered ring orifices. The high reactivity of the bridgehead double bonds was estimated by π-orbital axis vector (POAV) analysis comparing the bisfulleroid derivatives 5d, 5e, 6d, and 6e.

  硅烷修饰的氮杂环富勒烯 1b 和 1c 经过光氧合反应后，在 11 或 15 元环孔口上产生了具有酮内酰胺 2b 和 2c 或二酮亚胺 3b 和 3c 官能团的开笼富勒烯。通过对双富勒烯衍生物 5d、5e、6d 和 6e 进行π-轨道轴矢量（POAV）分析，估计桥头双键具有很高的反应活性。