bis(methoxy)iron(III) tetraphenylporphyrin(1-) | 89709-81-9

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: bis(methoxy)iron(III) tetraphenylporphyrin(1-)
• 英文别名: dimethoxo(tetraphenylporphinato)ferrate(III)；dimethoxo(tetraphenylporphinato)ferrate(III)(1-)
• CAS: 89709-81-9
• 化学式: C₄₆H₃₄FeN₄O₂
• 分子量: 730.649
• InChiKey: XHNQGIIKQHVQTH-NBICUONBSA-N

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：

  bis(methoxy)iron(III) tetraphenylporphyrin(1-) 在 n-butylhydroperoxide 作用下， 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  Autoreduction of a six-coordinate Fe(III)TPP-peroxide complex by heterolytic ironoxygen bond cleavage

  摘要：

  ESR, optical and NMR measurements have been carried out to study the reactions occurring between Fe(III)TPP(-OCH3)2 (Complex A) and t- or n-butylhydroperoxide in DMSO. The addition of t- or n-BHPO to complex A, in aerobic conditions, caused a marked shift of the absorption maxima, and resulted in the disappearance of the ESR signal due to the formation of diamagnetic species. The observed optical spectrum of the new iron complex (complex B) is explained as the Fe(II)TPP(-OCH3)2 species. In addition, the results of NMR measurements justified that complex B takes the ferrous low-spin state (S=0). The presence of an intermediate species (complex C), in the reduction processes of complex A to B, was demonstrated by means of simultaneous ESR and optical measurements, combined with the rapid mixing and freezing treatment. From comparison of the optical and ESR parameters of complex C and related iron complexes, the complex was ascribed to be six-coordinate Fe(III)TPP(-OCH3)(-OO-butyl), in which the deprotonated peroxide anion binds at the axial position. After standing the reaction mixture at 298 K for about 1 min, the ESR signal due to complex C disappeared, and an identical optical spectrum to complex B was observed. This means that the Fe(III)TPP-peroxide complex can be reduced to complex B, in which it is in the ferrous low-spin state. Based on these observation results, a possible reaction mechanism for autoreduction of complex C will be discussed.

  DOI：

  10.1016/s0020-1693(00)85823-5
• 作为产物：
  描述：

  meso-tetraphenylporphyrin iron(III) chloride 、 sodium methylate 以 甲醇 、 甲苯 为溶剂， 生成 bis(methoxy)iron(III) tetraphenylporphyrin(1-)
  参考文献：
  名称：

  Otsuka, Tomoko; Ohya, Toshie; Sato, Mitsuo, Inorganic Chemistry, 1984, vol. 23, # 12, p. 1777 - 1779

  摘要：

  DOI：

文献信息

• Models of the Low-Spin Iron(III) Hydroperoxide Intermediate of Heme Oxygenase:  Magnetic Resonance Evidence for Thermodynamic Stabilization of the d<i>_x</i><i>_y</i> Electronic State at Ambient Temperatures
  作者：Mario Rivera、Gregori A. Caignan、Andrei V. Astashkin、Arnold M. Raitsimring、Tatjana Kh. Shokhireva、F. Ann Walker

  DOI：10.1021/ja017334o

  日期：2002.5.1

  electron configurations and ring conformations may also exist in equilibrium in the enzymatic systems. The ruffled porphyrinate ring would aid the attack of the terminal oxygen of the hydroperoxide intermediate of heme oxygenase (HO) on the meso-carbon, and the large spin density at the meso-carbons of a d(xy) electron configuration heme suggests the possibility of a radical mechanism for HO. The dynamic

  在这项工作中进行的 [meso-(13)C-TPPFe(OCH(3))(OO(t)Bu)](-) 的 (13)C 脉冲 ENDOR 和 NMR 研究表明，尽管低-含有 ROO(-) 配体的自旋铁血红素位于 8 K 的 ad(pi) 轨道，d(xy) 电子构型在生理温度下是有利的。变温 NMR 谱表明一种动态情况，其中具有 ad(pi) 电子构型和平面卟啉环的血红素与具有皱褶卟啉环的 ad(xy) 电子构型处于平衡状态。由于血红素加氧酶的氢过氧化物复合物、细胞色素 P450 和本文报道的模型血红素复合物的 EPR 光谱的相似性，这两种电子构型和环构象也可能在酶促系统中处于平衡状态。皱褶的卟啉环将有助于血红素加氧酶 (H2O) 氢过氧化物中间体的末端氧对介碳的攻击，并且 ad(xy) 电子构型血红素的介碳处的大自旋密度表明可能 的根本机制。在模型复合物中观察到的皱褶 (d(xy)) 和平面
• Otsuka, Tomoko; Ohya, Toshie; Sato, Mitsuo, Inorganic Chemistry, 1985, vol. 24, # 5, p. 776 - 782
  作者：Otsuka, Tomoko、Ohya, Toshie、Sato, Mitsuo

  DOI：——

  日期：——