(fluorido)(5,10,15,20-tetramesitylporphyrinato)iron(III) | 155145-20-3

• 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: (fluorido)(5,10,15,20-tetramesitylporphyrinato)iron(III)
• 英文别名: Fe[5,10,15,20-tetramesitylporphyrinato]F；(TMP)FeF；(5,10,15,20-tetramesitylporphyrinato)Fe(III)F；[Fe(III)(meso-tetramesitylporphyrin)F]；Fe(TMP)F
• CAS: 155145-20-3
• 化学式: C₅₆H₅₂FFeN₄
• 分子量: 855.901
• InChiKey: CABDLFVUPLFZLQ-WSJWEZPUSA-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：

  (fluorido)(5,10,15,20-tetramesitylporphyrinato)iron(III) 在 臭氧 作用下， 以 二氯甲烷-D2 为溶剂， 生成 fluorido(5,10,15,20-tetramesitylporphyrinato(1-))oxoiron(IV)
  参考文献：
  名称：

  Gross, Zeev; Nimri, Shay, Inorganic Chemistry, 1994, vol. 33, # 9, p. 1731 - 1732

  摘要：

  DOI：
• 作为产物：
  描述：

  fluorido(5,10,15,20-tetramesitylporphyrinato(1-))oxoiron(IV) 在 cyclooctene 作用下， 以 二氯甲烷 为溶剂， 生成 (fluorido)(5,10,15,20-tetramesitylporphyrinato)iron(III)
  参考文献：
  名称：

  Effect of the Axial Ligand on the Reactivity of the Oxoiron(IV) Porphyrin π-Cation Radical Complex: Higher Stabilization of the Product State Relative to the Reactant State

  摘要：

  The proximal heme axial ligand plays an important role in tuning the reactivity of oxoiron(IV) porphyrin pi-cation radical species (compound I) in enzymatic and catalytic oxygenation reactions. To reveal the essence of the axial ligand effect on the-reactivity, we investigated it from a thermodynamic viewpoint. Compound I model complexes, (TMP+center dot)(FeO)-O-IV(L) (where TMP is 5,10,15,20-tetrarnesitylporphyrin and TMP+center dot is its pi-cation radical), can be provided with altered reactivity by changing the identity of the axial ligand, but the reactivity is not correlated with spectroscopic data (nu(Fe=O), redox potential, and so on) of (TMP+center dot)(FeO)-O-IV(L). Surprisingly, a clear correlation was found between the reactivity of (TMP+center dot)(FeO)-O-IV(L) and the Fe-II/Fe-III redox potential of (TMP)(FeL)-L-III, the final reaction product. This suggests that the thermodynamic stability of (TMP)(FeL)-L-III is involved in the mechanism of the axial ligand effect. Axial ligand-exchange experiments and theoretical calculations demonstrate a linear free-energy relationship, in which the axial ligand modulates the reaction free energy by changing the thermodynamic stability of (TMP)Fe-III(L) to a greater extent than (TMP+center dot)(FeO)-O-IV(L). The linear free energy relationship could be found for a wide range of anionic axial ligands and for various types of reactions, such as epoxidation, demethylation, and hydrogen abstraction reactions. The essence of the axial ligand effect is neither the electron donor ability of the axial ligand nor the electron affinity of compound I, but the binding ability of the axial ligand (the stabilization by the axial ligand). An axial ligand that binds more strongly makes (TMP)Fe-III(L) more stable and (TMP+center dot)(FeO)-O-IV(L) more reactive. All results indicate that the axial ligand controls the reactivity of compound I (the stability of the transition state) by the stability of the ground state of the final reaction product and not by compound I itself.

  DOI：

  10.1021/ic3006597

文献信息

• One-electron oxidized product of difluoroiron(iii) porphyrin: is it iron(iv) porphyrin or iron(iii) porphyrin π-cation radical?
  作者：Akira Ikezaki、Masashi Takahashi、Mikio Nakamura

  DOI：10.1039/c1dt10561b

  日期：——

  The electronic structure of [Fe(TMP)F2], which is formally a one-electron oxidation equivalent above [FeIII(TMP)F2]−, has been examined in solution by 1H NMR, UV-Vis, and Mössbauer spectroscopy. In CD2Cl2–CD3OD solution at 193 K, the pyrrole-H and m-H signals appeared at 128.2 and 116.7 ppm, respectively. The UV-Vis spectrum showed broad absorption bands at 560–680 nm. The Mössbauer spectrum taken

  [Fe（TMP）F 2 ]的电子结构在溶液中已通过1 H NMR，UV-Vis和Mössbauer检验，它的形式正式为高于[Fe III（TMP）F 2 ] -的单电子氧化当量。光谱学。在193 K的CD 2 Cl 2 –CD 3 OD溶液中，吡咯H和m H信号分别出现在128.2和116.7 ppm处。UV-Vis光谱显示在560–680 nm处有较宽的吸收带。冷冻获得的Mössbauer光谱甲苯–甲醇溶液表现出非常宽的单线，通过计算机模拟确定的IS和QS值分别为0.50和0.14 mm s -1。根据这些结果得出结论，[Fe（TMP）F 2 ] -的单电子氧化产物应配制成铁（III）自由基阳离子[Fe III（TMP˙）F 2 ]，而不是如先前所建议的以铁（IV）卟啉[Fe IV（TMP）F 2 ]的形式存在。
• Studies of Iron(III) Porphyrinates Containing Silanethiolate Ligands
  作者：Daniel J. Meininger、Jonathan D. Caranto、Hadi D. Arman、Zachary J. Tonzetich

  DOI：10.1021/ic401467k

  日期：2013.11.4

  The chemistry of several iron(III) porphyrinates containing silanethiolate ligands is described. The complexes are prepared by protonolysis reactions of silanethiols with the iron(III) precursors, [Fe(OMe)(TPP)] and [Fe(OH)(H2O)(TMP)] (TPP = dianion of meso-tetraphenylporphine; TMP = dianion of meso-tetramesitylporphine). Each of the compounds has been fully characterized in solution and the solid

  描述了几种含有硅烷硫醇配体的铁 (III) 卟啉酸盐的化学反应。该络合物通过与铁（III）前体的silanethiols反应质子分解制备的[Fe（OME）（TPP）]和[铁（OH）（H 2 O）（TMP）]（TPP =二价阴离子的内消旋-四苯基卟; TMP = 中四亚甲基卟啉的二价阴离子）。每种化合物都已在溶液和固体状态下得到充分表征。硅烷硫醇盐络合物相对于其他含有硫基配体的卟啉铁 (III) 络合物的稳定性允许检查它们与几种生物相关小分子（包括 H 2）的反应性S、NO 和 1-甲基咪唑。在电化学上，硅烷硫醇盐络合物在比类似芳烃硫醇盐络合物观察到的电位更高的电位下显示出准可逆的单电子氧化事件。讨论了这些配合物与其他硫连接的铁 (III) 卟啉酸盐的行为。
• Identification of high-valent fluoroiron porphyrin intermediates associated with the electrocatalytic functionalization of hydrocarbons
  作者：David L. Hickman、Alaganandan. Nanthakumar、Harold M. Goff

  DOI：10.1021/ja00227a019

  日期：1988.9