(m-chlorobenzoate)iron(III) 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin | 146082-00-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (m-chlorobenzoate)iron(III) 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin
• 英文别名: (TDCPP)Fe(III)(m-CBA)；(m-chlorobenzoato)(5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinato)iron(III)
• CAS: 146082-00-0
• 化学式: C₅₁H₂₄Cl₉FeN₄O₂
• 分子量: 1099.7
• InChiKey: ZZAFLRHGGYCJKB-TXFZNMFQSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 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：

  (m-chlorobenzoate)iron(III) 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin 在 4-硝基过氧化苯甲酸 、 3-氯苯甲酸 作用下， 以 二氯甲烷 为溶剂， 以90%的产率得到5,10,15,20-tetra(2,6-dichlorophenyl)porphyriniron(IV)oxo
  参考文献：
  名称：

  铁卟啉配合物催化单氧化反应的新型活性中间体

  摘要：

  FeIII(tdcpp) (1b) [tdcpp: 5,10,15,20-四(2,6-二氯苯基)卟啉]与氧化剂反应制备了新型高价氧杂铁卟啉(3b)如对硝基过苯甲酸和五氟碘代苯，在 -90 °C 的 CH2Cl2 中，在少量甲醇的存在下。3b 的紫外-可见光谱（λmax 在 418 和 550 nm 附近）类似于 O=FeIV(tdcpp)（4b，λmax 419, 543 nm）。然而，用碘离子滴定 3b 表明 3b 的氧化态是由铁 (III) 态双电子氧化而成的。此外，即使在-90°C 下，3b 也能催化烯烃（如苯乙烯）的氧化。氘核磁共振观察很容易排除 3b 作为 π 阳离子自由基的可能公式。3b 的溶液磁化率 (μeff = 4.0 ± 0.2 μB) 表明 3b 具有三个不成对电子。这些结果表明 3b 的正式描述是 O=Fe(V) 卟啉或·O-Fe(IV) 卟啉的高自旋配合物。在不存在的情况下

  DOI：

  10.1246/bcsj.71.1343
• 作为产物：
  描述：

  hydroxo(5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinato)iron(III) 、 3-氯苯甲酸 以 苯 为溶剂， 生成 (m-chlorobenzoate)iron(III) 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin
  参考文献：
  名称：

  Acylperoxo-Iron(III) Porphyrin Complexes: A New Entry of Potent Oxidants for the Alkene Epoxidation

  摘要：

  Competitive epoxidation of norbornylene and alpha-methylstyrene by peracids in the presence of iron porphyrins has been carried out in methylene chloride and toluene at -78 degrees C. When (TMP)Fe-III(RCO(2)) (TMP = 5,10,15,20-tetramesitylporphyrin) is used as a catalyst in methylene chloride, selectivity of norbornylene oxide over alpha-methylstyrene oxide is almost identical even though a variety of peracids are used, since O=Fe(IV)TMP pi-cation radical 2a is the common oxidant in the reactions. On the other hand, the selectivity in the epoxidations catalyzed by (TDCPP)Fe-III(X) (TDCPP: 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin is found to be dependent on the structure of peracids. The latter type of the results is also obtained for the reactions catalyzed both by (TMP)Fe-III(X) and by (TDCPP)Fe-III(X) in toluene. The dependence of the selectivity in the epoxidation on the structure of peracids is attributed to the alteration of the oxidant from 2 to peracid-Fe(III) complexes 1. The direct involvement of 1 in the epoxidation has been further confirmed by spectroscopic studies of the reactions. Under the catalytic epoxidation conditions at low temperature, the participation of 1 and 2 as the active species is controlled either by electronic structure of iron porphyrin complexes (push-pull effect) or by alteration of the solvent.

  DOI：

  10.1021/ja00130a007

文献信息

• Acid-catalyzed disproportionation of oxoiron(IV) porphyrins to give oxoiron(IV) porphyrin radical cations
  作者：Zhengzheng Pan、Martin Newcomb

  DOI：10.1016/j.inoche.2011.03.044

  日期：2011.6

  Disproportionation of oxoiron(IV) porphyrin (Compound II) to oxoiron(IV) porphyrin radical cation (Compound I) was studied in three P450 model systems with different electronic structures. Direct conversion of Compound II to Compound I has been observed for 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin (TDCPP) in acid-catalyzed reactions in a mixed solvent of acetonitrile and water (1:1, v/v) containing

  在具有不同电子结构的三个 P450 模型系统中研究了氧化铁 (IV) 卟啉（化合物 II）与氧化铁 (IV) 卟啉自由基阳离子（化合物 I）的歧化。在乙腈和水的混合溶剂 (1:1, v/v) 含有过量的 m-CPBA 氧化剂，二级速率常数为 (1.3 ± 0.2) × 10(2) M(-1) s(-1)。酸催化歧化在很大程度上取决于卟啉大环上取代芳基的电子需求。三个卟啉系统的歧化平衡常数显示出剧烈的变化。
• Preparation and characterization of an oxo–iron(<scp>V</scp>)–porphyrin complex
  作者：Kazuya Yamaguchi、Yoshihito Watanabe、Isao Morishima

  DOI：10.1039/c39920001721

  日期：——

  The novel complex OFeV(tdcpp)3, which is prepared by the addition of methanol to a methylene chloride solution of the corresponding OFeIV(tdcpp) cation radical in CH2Cl2 at –90°C, has been characterized on the basis of UV–VIS, ESR, and deuterium NMR spectroscopy.

  OFeV(tdcpp)3是一种新型化合物，通过在-90°C下向CH2Cl2中相应的OFeIV(tdcpp)阳离子自由基的二氯甲烷溶液中添加甲醇制备而成，其特性已通过紫外-可见光、电子自旋共振和氘核磁共振光谱测定。