6-isocyanoazulene | 529475-47-6

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 6-isocyanoazulene
• CAS: 529475-47-6
• 化学式: C₁₁H₇N
• 分子量: 153.183
• InChiKey: ABAGTQPHQTZHRH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  4.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  6-isocyanoazulene 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 hexakis(6-isocyanoazulene)chromium(I) tetrafluoroborate
  参考文献：
  名称：

  First Isocyanoazulene and Its Homoleptic Complexes

  摘要：

  An efficient synthesis of remarkably stable 6-isocyanoazulene (CN6Az), the first nonbenzenoid organic isocyanide, is described. Its superb pi-accepting potential as a ligand was demonstrated through cyclic voltammetry studies on the binary complexes [Cr(CN6Az)6]0/+. The paramagnetic shift patterns for [Cr(CN6Az)6]+, the only azulenic pi-system studied by paramagnetic NMR, suggest that Cr(dpi) --> CN6Az(ppi*) electron delocalization involves both rings of the azulenyl substituents in [Cr(CN6Az)6]+. This conclusion is supported by density functional theory calculations on the complex [Cr(CN6Az)6][BF4].

  DOI：

  10.1021/ja034706f
• 作为产物：
  描述：

  6-aminoazulene 在 N,N-二异丙基乙胺 、 三氯氧磷 作用下， 以 二氯甲烷 为溶剂， 反应 0.42h， 生成 6-isocyanoazulene
  参考文献：
  名称：

  First Isocyanoazulene and Its Homoleptic Complexes

  摘要：

  An efficient synthesis of remarkably stable 6-isocyanoazulene (CN6Az), the first nonbenzenoid organic isocyanide, is described. Its superb pi-accepting potential as a ligand was demonstrated through cyclic voltammetry studies on the binary complexes [Cr(CN6Az)6]0/+. The paramagnetic shift patterns for [Cr(CN6Az)6]+, the only azulenic pi-system studied by paramagnetic NMR, suggest that Cr(dpi) --> CN6Az(ppi*) electron delocalization involves both rings of the azulenyl substituents in [Cr(CN6Az)6]+. This conclusion is supported by density functional theory calculations on the complex [Cr(CN6Az)6][BF4].

  DOI：

  10.1021/ja034706f

文献信息

• Positional Isomers of Isocyanoazulenes as Axial Ligands Coordinated to Ruthenium(II) Tetraphenylporphyrin: Fine-Tuning Redox and Optical Profiles
  作者：Mahtab Fathi-Rasekh、Gregory T. Rohde、Mason D. Hart、Toshinori Nakakita、Yuriy V. Zatsikha、Rashid R. Valiev、Mikhail V. Barybin、Victor N. Nemykin

  DOI：10.1021/acs.inorgchem.9b01030

  日期：2019.7.15

  compressed tetragonal geometry. The redox properties of the new compounds were assessed by electrochemical and spectroelectrochemical means and correlated with the electronic structures predicted by density functional theory and CASSCF calculations. Both experimental and theoretical data are consistent with the first two reduction processes involving the axial azulenic ligands, whereas the oxidation profile

  分离并表征了具有轴向配位氧化还原活性，低光学间隙的2-或6-异氰基腈配体的两种异构钌（II）/ 5,10,15,20-四苯基卟啉配合物，并通过NMR，UV-vis和磁性圆进行了表征二色性（MCD）光谱方法，高分辨率质谱和单晶X射线晶体学。UV-vis和MCD光谱支持在卟啉生色团的Q波段区域中存在低能，以azulene为中心的跃迁。新L 2中的第一个协调领域RuTPP络合物反映了压缩的四边形几何形状。通过电化学和光谱电化学方法评估了新化合物的氧化还原性质，并将其与密度泛函理论和CASSCF计算所预测的电子结构相关联。实验和理论数据均与涉及轴向天青石配体的前两个还原过程一致，而氧化曲线（在增加电位的方向上）是由钌离子，卟啉核和轴向天青石部分施加的。
• Five Possible Isocyanoazulenes and Electron-Rich Complexes Thereof:  A Quantitative Organometallic Approach for Probing Electronic Inhomogeneity of the Azulenic Framework
  作者：Randall E. Robinson、Thomas C. Holovics、Stephan F. Deplazes、Douglas R. Powell、Gerald H. Lushington、Ward H. Thompson、Mikhail V. Barybin

  DOI：10.1021/om0502180

  日期：2005.5.1

  Efficient syntheses of all five possible isocyanoazulenes, the four isomeric archetypal compounds CN(1)Az, CN(2)Az, CN(4)Az, and CN(6)Az, as well as the 1,3-di-tert-butyl derivative of CN(5)Az (Az = azulenyl), are described. Compounds CN(1)Az and CN(2)Az show unexpected shifts of the S-0 -> S-1 transition in their electronic spectra relative to azulene. The origins of these "anomalous" shifts have been addressed by DFT calculations, cyclic voltammetry, and comparison of the electronic spectra of isocyanoazulenes with those of the corresponding isomeric cyanoazulenes. Despite the high propensity of the azulenic nucleus to undergo multihapto coordination and C-C coupling in the presence of low-valent metals, the isocyanoazulenes react with 1/6 equiv of Cr(eta(6)-naphthalene)(2) to afford thermally stable Cr(CN(x)Az)(6) (x = 1, 2, 4, 6), which contain six discrete azulenyl groups separated from the Cr center by isocyanide linkers. All Cr(CN(x)Az)(6) species undergo oxidation to form the corresponding paramagnetic cations [Cr(CN(x)Az)(6)](+), which have been crystallographically characterized. Changing the atom of attachment of the azulenyl groups to the "Cr(CN)(6)" core substantially alters the donor/acceptor properties of the isocyanoazulene ligands. The half-wave Cr0/+ and Cr+/2+ redox potentials for [Cr(CN(x)Az)(6)](z) form the "electrochemical series" that constitutes a quantitative measure of electronic inhomogeneity of the azulenic framework. Unpaired spin delocalization within the azulenic moieties of [Cr(CN(x)Az)(6)](+) has been observed by multinuclear NMR. The Cr-I(d pi)-> CN(x)Az(p pi*) interaction has been shown to be an important contributor to the mechanism of unpaired electron delocalization in [Cr(CN(x)Az)(6)](+).