cyanopentaamminechromium(III) chloride | 72509-67-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 三嗪类
• 英文名称: cyanopentaamminechromium(III) chloride
• CAS: 72509-67-2
• 化学式: CH₁₅CrN₆*2Cl
• 分子量: 234.072
• InChiKey: BFHMQRISIFYGEU-UHFFFAOYSA-M

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：

  cyanopentaamminechromium(III) chloride 、 sodium perchlorate 以 水 为溶剂， 以40%的产率得到cyanopentaamminechromium(III) perchlorate
  参考文献：
  名称：

  Cyanopentaamminechromium(III). Synthesis, characterization, and aquation kinetics

  摘要：

  DOI：

  10.1021/ic50206a013
• 作为产物：
  描述：

  [Cr(dimethylsulfoxide)(NH3)5](ClO4)3 在 sodium cyanide 、 LiCl 作用下， 以 二甲基亚砜 为溶剂， 以65%的产率得到cyanopentaamminechromium(III) chloride
  参考文献：
  名称：

  Cyanopentaamminechromium(III). Synthesis, characterization, and aquation kinetics

  摘要：

  DOI：

  10.1021/ic50206a013

文献信息

• Analysis of d–d Transitions in [Cr(CN)(NH₃)₅]²⁺as Inferred from Polarized Optical Spectra and Angular Overlap Model Calculations
  作者：Akio Urushiyama、Mutsuyoshi Itoh、Thomas Schönherr

  DOI：10.1246/bcsj.68.594

  日期：1995.2

  The polarized single-crystal absorption spectra of [Cr(CN)(NH3)5]Cl(ClO4) were measured for interconfigurational quartet (t2g3 → t2g2eg) and intraconfigurational doublet transitions (t2g3 → t2g3). The band splittings of the spin-allowed transitions, 4A2g → 4T2g,4T1g, were derived to 600—1000 cm−1 from a Gaussian band deconvolution of the σ and π spectra. At low temperature (77 K), more than 45 sharp bands could be detected in the intercombination band region of the lowest doublets (2Eg, 2T1g), which were completely assigned to the five possible zero-phonon transitions and corresponding vibronic sidebands. The vibrational frequencies due to the electronic ground state were obtained from the infrared spectrum and by measuring the emission lines under resonant excitation, providing us with a sufficient data base for a normal coordinate treatment of the pentaamminecyano cation. The d-energy level scheme is rationalized using the angular overlap model (AOM). Geometric parameters were obtained from an X-ray analysis of the chloride–perchloride salt, which shows a cation of approximately 4mm (C4v) site symmetry, consistent with a linearly coordinated cyano group. The AOM parameters evaluated for the CN- ligand show strong σ-antibonding (eσ = ca. 7500 cm−1) together with unusually larger π-bonding (eπ = ca. −900 cm−1), which both contribute to the extremely high value of the respective ligand field parameter Dq. The large splitting of the lowest doublet state, 2Eg (Oh), has been shown to originate from a low-symmetry effect in the treatment of interelectronic repulsion. The attributed tetragonal orbital expansion parameter (τ = 0.99) was calculated to be similar to values recently obtained for related pentaammineaniono complexes.

  对[Cr(CN)(NH3)5]Cl(ClO4)的偏振单晶吸收光谱进行了配置间四重跃迁（t2g3 → t2g2eg）和配置内二重跃迁（t2g3 → t2g3）的测量。自旋允许的跃迁（4A2g → 4T2g、4T1g）的波段分裂是通过对 σ 和 π 光谱进行高斯波段去卷积得到的，波段分裂范围为 600-1000 cm-1。在低温（77 K）下，可以在最低双音（2Eg、2T1g）的结合带区域检测到超过 45 个尖锐带，这些带完全归属于五个可能的零声子跃迁和相应的振子边带。通过红外光谱和测量共振激发下的发射线，我们获得了电子基态的振动频率，这为我们对五氨基氰阳离子进行正坐标处理提供了充分的数据基础。利用角度重叠模型（AOM）对 d 能级方案进行了合理化。几何参数是通过对氯盐酸盐的 X 射线分析获得的，该分析表明阳离子的位点对称性约为 4mm（C4v），与线性配位的氰基一致。为 CN- 配体评估的 AOM 参数显示出很强的σ-反键（eσ = 约 7500 cm-1）和异常大的π-键（eπ = 约 -900 cm-1），这两个参数都导致了相应配体场参数 Dq 的极高值。最低双态 2Eg (Oh) 的大分裂已被证明是在处理电子间斥力时产生的低对称效应所致。计算得出的四方轨道膨胀参数（τ = 0.99）与最近在相关五丙胺络合物中获得的数值相似。