(2,3,7,8,12,13,17,18-tetraethylporphyrinato)Fe(III)(C6F4H) | 96482-32-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四吡咯及其衍生物
• 英文名称: (2,3,7,8,12,13,17,18-tetraethylporphyrinato)Fe(III)(C6F4H)
• CAS: 96482-32-5
• 化学式: C₆HF₄*C₃₆H₄₄N₄*Fe
• 分子量: 737.687
• InChiKey: DMPFWLCVJZYSJZ-WSZPVVFGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.95
• 重原子数：
  51.0
• 可旋转键数：
  8.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  53.98
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (2,3,7,8,12,13,17,18-tetraethylporphyrinato)Fe(III)(C6F4H) 在 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  Kinetic and Thermodynamic Studies of Iron(III) and Iron(IV) σ-Bonded Porphyrins. Formation and Reactivity of [(OEP)Fe(R)]ⁿ⁺, Where OEP Is the Dianion of Octaethylporphyrin (n = 0, 1, 2, 3) and R = C₆H₅, 3,4,5-C₆F₃H₂, 2,4,6-C₆F₃H₂, C₆F₄H, or C₆F₅

  摘要：

  A series of high-and low-spin iron(III) phenyl and fluorophenyl octaethylporphyrin complexes are characterized by their electrochemical and spectroscopic properties in nonaqueous media. The investigated compounds are represented as (OEP)Fe(R), where R = C6H5, 3,4,5-C6F3H2, 2,4,6-C6F3H2, C6F4H, or C6F5 and OEP is the dianion of 2,3,7,8,12,13,17, 18-octaethylporphyrin. The two C6F3H2 complexes are of special interest in that these isomers differ in the spin state of the iron(III). Electrochemical studies indicate that three one-electron oxidations are seen for all of the (OEP)Fe(R) derivatives which were investigated both at room and low temperature under conditions where migration of the sigma-bonded ligand does not occur an the time scale of the experiment. The first one-electron oxidation of each compound leads to an Fe(IV) porphyrin, and this is followed by a migration of the axial group from the iron center to one of the four nitrogen atoms independent of the nature of the axial group or the iron(III) spin state. The kinetics were examined to evaluate the migration rate constants in the presence and absence of pyridine as a sixth axial ligand. The results of this study show that the stronger the electron donor ability of the R group, the faster the migration rate in the case of the five-coordinate species. However, an increase in charge density at the metal center by axial coordination of pyridine retards the migration rate and this result is interpreted in terms of a rate determining electron transfer step from R to Fe(IV) of the singly oxidized species prior to the migration. Our results also show that the spin state of the iron(III) octaethylporphyrin is not a key factor which governs the migration of the axial ligand of the electrooxidized species. For the first time, an overall mechanism is proposed to explain the migration reaction in the sigma-bonded iron porphyrin complexes.

  DOI：

  10.1021/ic9714706

文献信息

• Guilard; Lagrange; Tabard, Inorganic Chemistry, 1985, vol. 24, # 22, p. 3649 - 3656
  作者：Guilard、Lagrange、Tabard、Lançon、Kadish

  DOI：——

  日期：——