hexakis(2-isocyanoazulene)chromium(0) | 853059-37-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: hexakis(2-isocyanoazulene)chromium(0)
• CAS: 853059-37-7
• 化学式: C₆₆H₄₂CrN₆
• 分子量: 971.096
• InChiKey: NQLUSSHKIDKRNS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  hexakis(2-isocyanoazulene)chromium(0) 、 silver tetrafluoroborate 以 二氯甲烷 为溶剂， 以76%的产率得到hexakis(2-isocyanoazulene)chromium(I) tetrafluoroborate
  参考文献：
  名称：

  Five Possible Isocyanoazulenes and Electron-Rich Complexes Thereof:  A Quantitative Organometallic Approach for Probing Electronic Inhomogeneity of the Azulenic Framework

  摘要：

  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)](+).

  DOI：

  10.1021/om0502180
• 作为产物：
  描述：

  bis(η6-naphthalene)chromium(0) 、 2-isocyanoazulene 以 四氢呋喃 为溶剂， 以94%的产率得到hexakis(2-isocyanoazulene)chromium(0)
  参考文献：
  名称：

  Five Possible Isocyanoazulenes and Electron-Rich Complexes Thereof:  A Quantitative Organometallic Approach for Probing Electronic Inhomogeneity of the Azulenic Framework

  摘要：

  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)](+).

  DOI：

  10.1021/om0502180