(nitrato)(5,10,15,20-tetramesitylporphyrinato)iron(III) | 258828-91-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: (nitrato)(5,10,15,20-tetramesitylporphyrinato)iron(III)
• 英文别名: (5,10,15,20-tetramesitylporphyrinato)Fe(III)(nitrato)；(5,10,15,20-tetramesitylporphyrinato)Fe(NO3)；(TMP)Fe(NO3)；Fe(TMP)(NO3)
• CAS: 258828-91-0
• 化学式: C₅₆H₅₂FeN₅O₃
• 分子量: 898.908
• InChiKey: GYLWBEZNVYXWPH-WSJWEZPUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  14.04
• 重原子数：
  65.0
• 可旋转键数：
  4.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  120.18
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  (nitrato)(5,10,15,20-tetramesitylporphyrinato)iron(III) 、 臭氧 以 二氯甲烷 为溶剂， 生成 nitrate(5,10,15,20-tetramesitylporphyrinato(1-))oxoiron(IV)
  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
• 作为产物：
  描述：

  nitrate(5,10,15,20-tetramesitylporphyrinato(1-))oxoiron(IV) 在 1,4-cyclohexadiene or N,N-dimethyl-p-nitroaniline 作用下， 以 二氯甲烷 为溶剂， 生成 (nitrato)(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

• Models of Nitric Oxide Synthase:  Iron(III) Porphyrin-Catalyzed Oxidation of Fluorenone Oxime to Nitric Oxide and Fluorenone
  作者：Charles C.-Y. Wang、Douglas M. Ho、John T. Groves

  DOI：10.1021/ja992373+

  日期：1999.12.1

  unusual reaction, iron porphyrin-catalyzed oxygenations of oximes with O2 were investigated. The oxidation of fluorenone oxime and a stoichiometric amount of hydroxoiron(III) porphyrin (Fe(OH)P, P = TMP and TPFPP) with O2 in benzene generated Fe(NO)P, fluorenone, and O-(9-nitro-9-fluorenyl)fluorenone oxime. The X-ray crystal structure of the oxime ether product suggests that it originated from the dimerization

  一氧化氮合酶 (NOS) 是一种含血红素的单加氧酶，可分两步催化 L-精氨酸氧化为 L-瓜氨酸和 NO。在 NOS 反应的第二步中，瓜氨酸和 NO 是由血红素催化的 1N-羟基精氨酸的 3-电子氧化产生的。为了模拟这种不寻常的反应，研究了铁卟啉催化的肟与 O2 的氧化作用。在苯中用 O2 氧化芴酮肟和化学计量的羟铁 (III) 卟啉（Fe(OH)P，P = TMP 和 TPFPP），生成 Fe(NO)P、芴酮和 O-(9-nitro-9) -芴基)芴酮肟。肟醚产物的 X 射线晶体结构表明它源于芴基亚胺氧基自由基的二聚化。该反应的详细分析表明，肟首先与 Fe(OH)P 反应生成 5-配位，高自旋肟化铁 (III) 卟啉 [Fe(oximate)P]。肟化铁(III)四(2,6-二氯苯基)卟啉[Fe(肟酸)TDC的X射线晶体结构...
• Factors Affecting Hydrogen-Tunneling Contribution in Hydroxylation Reactions Promoted by Oxoiron(IV) Porphyrin π-Cation Radical Complexes
  作者：Zhiqi Cong、Haruki Kinemuchi、Takuya Kurahashi、Hiroshi Fujii

  DOI：10.1021/ic501737j

  日期：2014.10.6

  transfer with a tunneling effect (H-tunneling) has been proposed to be involved in aliphatic hydroxylation reactions catalyzed by cytochrome P450 and synthetic heme complexes as a result of the observation of large hydrogen/deuterium kinetic isotope effects (KIEs). In the present work, we investigate the factors controlling the H-tunneling contribution to the H-transfer process in hydroxylation reaction by

  由于观察到大的氢/氘动力学同位素效应（KIEs），已提出具有隧穿效应的氢原子转移（H隧道）参与了细胞色素P450和合成血红素配合物催化的脂肪族羟基化反应。在目前的工作中，我们通过研究氧代铁（oxoiron）在氧杂蒽（1,2,3,4-四氢萘）的苄基位置上的羟基化反应动力学，研究控制羟基化反应中H隧穿对H转移过程的控制因素。 IV）5,10,15,20-四氢卟啉π-阳离子自由基络合物（（TMP +•）Fe IVO（L））在单周转条件下。H-同位素异构体的这些羟基化反应的Arrhenius图具有向上凹的轮廓。D同位素异构体的Arrhenius图，清晰的等渗点和产物分析排除了凹轮廓中与热相关的其他反应过程的参与。这些结果为H-隧道参与限速H-转移过程提供了证据。这些轮廓是使用从Bell隧道模型导出的方程式进行模拟的。KIE值的温度依赖性（k H / k D对这些反应确定的）表明，随着反应温度降低，
• Effect of Imidazole and Phenolate Axial Ligands on the Electronic Structure and Reactivity of Oxoiron(IV) Porphyrin π-Cation Radical Complexes: Drastic Increase in Oxo-Transfer and Hydrogen Abstraction Reactivities
  作者：Akihiro Takahashi、Takuya Kurahashi、Hiroshi Fujii

  DOI：10.1021/ic802123m

  日期：2009.3.16

  oxoiron(IV) porphyrin π-cation radical complex was drastically increased by the imidazole and phenolate axial ligands. The reaction rate for cyclooctene epoxidation was increased 100- to 400-fold with axial coordination of imidazoles and phenolate. A similar increase was also observed for the oxidation of 1,4-cyclohexadiene,N,N-dimethyl-p-nitroaniline and hydrogen peroxide. These results suggest extreme enhancement

  为了研究轴向配体对过氧化物酶和过氧化氢酶化合物I的电子结构和反应性的影响，氧代铁（IV）卟啉π-阳离子自由基与咪唑，2-甲基咪唑，4（5）-甲基咪唑和3-氟-通过臭氧氧化5,10,15,20-四甲苯基卟啉（TMP）和2,7,12,17-四甲基-3,8,13,18-四甲卟啉（TMTMP）。这些配合物的特征是吸收，1 H，2 H和19F NMR，电子顺磁共振（EPR）和电喷雾电离质谱（ESI-MS）光谱。发现化合物I在约650nm处的特征吸收峰是评估轴向配体的电子给体效应的良好标志。轴向配体效应不会改变卟啉π阳离子的自由基状态，TMP配合物的2u态或TMTMP配合物和化合物I的1u自由基状态。有效地转移到a 2u络合物的轴向配体中，而不是a 1u络合物复合体。最重要的是，咪唑和酚盐轴向配体极大地提高了氧化铁（IV）卟啉π-阳离子自由基络合物的反应性。在咪唑和酚盐的轴向配位下，环辛烯环氧化的反应