chloro(meso-tetrakis(2,4,6-triethylphenyl)porphyrinato)iron(III) | 159436-72-3

• 英文名称: chloro(meso-tetrakis(2,4,6-triethylphenyl)porphyrinato)iron(III)
• 英文别名: [Fe(meso-tetrakis(2,4,6-triethylphenyl)porphyrinate)Cl]；(Fe(Et-TPP)Cl)
• CAS: 159436-72-3
• 化学式: C₆₈H₇₆ClFeN₄
• 分子量: 1040.68
• InChiKey: MJJWDVWHBJZQOP-KSUUBVDHSA-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：

  chloro(meso-tetrakis(2,4,6-triethylphenyl)porphyrinato)iron(III) 、 氰化四丁基铵 以 二氯甲烷-D2 为溶剂， 生成 [Fe(meso-tetrakis(2,4,6-triethylphenyl)porphyrinate)(CN)2](1-)
  参考文献：
  名称：

  Electron Configuration of Ferric Ions in Low-Spin (Dicyano)(meso-tetraarylporphyrinato)iron(III) Complexes

  摘要：

  The electron configuration of a series of low-spin (dicyano){meso-tetrakis(2,4,6-trialkylphenyl)porphyrinato}iron(III) complexes, [Fe(R-TPP)(CN)(2)](-) where R = Me, Et, or Pr-i, together with the parent [Fe(TPP)(CN)(2)](-), has been examined in dichloromethane-methanol solution by H-1 NMR, C-13 NMR, and EPR spectroscopies. While the ferric ion of [Fe(TPP)(CN)(2)](-) has shown a common (d(xy))(2)(d(xz),d(yz))(3) configuration, the ferric ions of the alkyl-substituted complexes [Fe(R-TPP)(CN)(2)](-) have exhibited the preference of a less common (d(xz),d(yz))(4)(d(xy))(1) configuration. Spectroscopic characteristics of the complexes in which ferric ions take the (d(xz),d(yz))(4)(d(xy))(1) configuration are (i) axial type EPR spectra, (ii) downfield shifted pyrrole and meta signals in H-1 NMR spectra, and (iii) downfield shifted meso-carbon signals in C-13 NMR spectra. Occurrence of the less common (d(xz),d(yz))(4)(d(xy))(1) configuration in [Fe(R-TPP)(CN)(2)](-) has been ascribed to the electronic interaction between iron (d(pi)) and cyanide (p(pi)*) orbitals. The interaction stabilizes the d(pi) orbitals and induces (d(xz),d(yz))(4)(d(xy))(1) configuration. Since the electron configuration of (dicyano){meso-tetrakis(2,6-dichlorophenyl)porphyrinato}iron(III), [Fe(Cl-TPP)(CN)(2)](-), which carries bulky electronegative chlorine atoms at the ortho positions, is presented as a common (d(xy))(2)(d(xz),d(yz))(3), the less common (d(xz),d(yz))(4)(d(xy))(1) configuration in [Fe(R-TPP)(CN)(2)](-) can be ascribed, at least partially, to the electron-donating ability of the meso-aryl groups.

  DOI：

  10.1021/ic990328x
• 作为产物：
  描述：

  iron(II) chloride tetrahydrate 、 5,10,15,20-tetrakis[2,4,6-triethylphenyl]-21H,23H-porphyrin 以 N,N-二甲基甲酰胺 为溶剂， 生成 chloro(meso-tetrakis(2,4,6-triethylphenyl)porphyrinato)iron(III)
  参考文献：
  名称：

  Electron Configuration of Ferric Ions in Low-Spin (Dicyano)(meso-tetraarylporphyrinato)iron(III) Complexes

  摘要：

  The electron configuration of a series of low-spin (dicyano){meso-tetrakis(2,4,6-trialkylphenyl)porphyrinato}iron(III) complexes, [Fe(R-TPP)(CN)(2)](-) where R = Me, Et, or Pr-i, together with the parent [Fe(TPP)(CN)(2)](-), has been examined in dichloromethane-methanol solution by H-1 NMR, C-13 NMR, and EPR spectroscopies. While the ferric ion of [Fe(TPP)(CN)(2)](-) has shown a common (d(xy))(2)(d(xz),d(yz))(3) configuration, the ferric ions of the alkyl-substituted complexes [Fe(R-TPP)(CN)(2)](-) have exhibited the preference of a less common (d(xz),d(yz))(4)(d(xy))(1) configuration. Spectroscopic characteristics of the complexes in which ferric ions take the (d(xz),d(yz))(4)(d(xy))(1) configuration are (i) axial type EPR spectra, (ii) downfield shifted pyrrole and meta signals in H-1 NMR spectra, and (iii) downfield shifted meso-carbon signals in C-13 NMR spectra. Occurrence of the less common (d(xz),d(yz))(4)(d(xy))(1) configuration in [Fe(R-TPP)(CN)(2)](-) has been ascribed to the electronic interaction between iron (d(pi)) and cyanide (p(pi)*) orbitals. The interaction stabilizes the d(pi) orbitals and induces (d(xz),d(yz))(4)(d(xy))(1) configuration. Since the electron configuration of (dicyano){meso-tetrakis(2,6-dichlorophenyl)porphyrinato}iron(III), [Fe(Cl-TPP)(CN)(2)](-), which carries bulky electronegative chlorine atoms at the ortho positions, is presented as a common (d(xy))(2)(d(xz),d(yz))(3), the less common (d(xz),d(yz))(4)(d(xy))(1) configuration in [Fe(R-TPP)(CN)(2)](-) can be ascribed, at least partially, to the electron-donating ability of the meso-aryl groups.

  DOI：

  10.1021/ic990328x

文献信息

• Effects of Solvents on the Electron Configurations of the Low-Spin Dicyano[<i>m</i><i>eso</i>-tetrakis(2,4,6-triethylphenyl)porphyrinato]iron(III) Complex:  Importance of the C−H···N Weak Hydrogen Bonding
  作者：Akira Ikezaki、Mikio Nakamura

  DOI：10.1021/ic0108383

  日期：2002.5.1

  isomers with different electron configurations. In fact, we have observed the unprecedented EPR spectra at 4.2 K which contain both the axial- and large g(max)-type signals in some solvents such as benzene, toluene, and acetonitrile. The observation of the two types of signals has been ascribed to the slow interconversion on the EPR time scale at 4.2 K between the ruffled complex with the (d(xz), d(yz))(4)(d(xy))(1)

  电子配置有两种类型，（d（xy））（2）（d（xz），d（yz））（3）和（d（xz），d（yz））（4）（d（xy ））（1），在低旋转铁（III）卟啉配合物中。为了揭示溶剂对基态电子构型的影响，我们研究了低旋转双氰基[间-四（2,4,6-三乙基苯基）卟啉]的（13）C-和（1）H-NMR谱。高铁酸盐（III）在各种溶剂中的使用，包括质子，偶极非质子和非极性溶剂。在NMR研究的基础上，我们得出以下结论：（i）配合物采用具有（d（xz），d（yz））（4）（d（xy））（1）电子的基态（d（xz），d（yz））（4）（d（xy）（））（1）基态在甲醇中，因为d（pi）轨道由于OH而稳定。配位氰化物和甲醇之间存在N氢键; （ii）该复合物还具有（d（xz），d（yz））（4）（d（xy））（1）在非极性溶剂（例如氯仿和二氯甲烷）中的基态，这归因于CH ... N使d（pi）轨道稳定配位氰化物与溶剂分子之间的氢键弱;