Fe(tetraphenylporphyrin)(imidazole)2 | 19599-08-7

• 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: Fe(tetraphenylporphyrin)(imidazole)2
• 英文别名: [Fe^II(5,10,15,20-tetraphenyl-21H,23H-porphine)(imidazole)₂]；[Fe^II(tpp)(ImH)₂]；[Fe(meso-tetraphenylporphyrinato)(imidazole)2]；[Fe(tpp)(ImH)2]
• CAS: 19599-08-7
• 化学式: C₅₀H₃₆FeN₈
• 分子量: 804.736
• InChiKey: BFQCIPJQQCZWIM-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：

  Fe(tetraphenylporphyrin)(imidazole)2 在 乙醇 作用下， 以 乙醇 为溶剂， 生成
  参考文献：
  名称：

  Photoinduced decarbonylation from carbonyliron tetraphenylporphyrin in ethanol: effects of axial imidazole studied by laser flash photolysis

  摘要：

  Photochemical reactions of carbonyliron(II) tetraphenylporphyrins, (CO)(L)FeIITPP (L = ethanol and imidazole) and bisimidazoleiron(II) tetraphenylporphyrin, (Im)2FeIITPP, in ethanol were systematically investigated by laser flash photolysis. The yields for photodissociation of CO from (CO)(C2H5OH)FeIITPP and (CO)(Im)FeIITPP were determined to be 0.53 and 0.9 at room temperature, respectively. On the basis of the quantum yield measurements in the temperature range 180-300 K, the activation energies for decarbonylation obtained for (CO)(C2H5OH)FeIITPP and (CO)(Im)FeIITPP were 0 and 4.9 kcal mol-1, respectively. No dissociation of the ligand L from (CO)(L)FeIITPP was detected. The photochemical dissociation of the axial imidazole from (IM)2FeIITPP was also studied. The yield for photodissociation of imidazole obtained was 0. 1 8 at room temperature, and the activation energy was evaluated to be 2.6 kcal mol-1. It was found that (Im)(C2H5OH)FeIITPP produced by photolysis of both (CO)(Im)FeIITPP and (IM)2FeIITPP undergoes spontaneous base elimination to give (C2H5OH)2FeIITPP and imidazole, Im. The reactive excited states responsible for photodissociation of the axial ligands as well as the spontaneous base elimination reaction are discussed in detail.

  DOI：

  10.1021/j100201a034
• 作为产物：
  描述：

  咪唑 、 meso-tetraphenylporphyrin iron(III) chloride 在 sodium tetrahydroborate 作用下， 以 四氢呋喃 为溶剂， 反应 48.5h， 生成 Fe(tetraphenylporphyrin)(imidazole)2
  参考文献：
  名称：

  Resonant Inelastic X-ray Scattering on Ferrous and Ferric Bis-imidazole Porphyrin and Cytochrome c: Nature and Role of the Axial Methionine–Fe Bond

  摘要：

  Axial CuS(Met) bonds in electron transfer (ET) active sites are generally found to lower their reduction potentials. An axial S(Met) bond is also present in cytochrome c (cyt c) and is generally thought to increase the reduction potential. The highly covalent nature of the porphyrin environment in heme proteins precludes using many spectroscopic approaches to directly study the Fe site to experimentally quantify this bond. Alternatively, L-edge X-ray absorption spectroscopy (XAS) enables one to directly focus on the 3d-orbitals in a highly covalent environment and has previously been successfully applied to porphyrin model complexes. However, this technique cannot be extended to metalloproteins in solution. Here, we use metal K-edge XAS to obtain L-edge like data through 1s2p resonance inelastic X-ray scattering (RIXS). It has been applied here to a bis-imidazole porphyrin model complex and cyt c. The RIXS data on the model complex are directly correlated to L-edge XAS data to develop the complementary nature of these two spectroscopic methods. Comparison between the bis-imidazole model complex and cyt c in ferrous and ferric oxidation states show quantitative differences that reflect differences in axial ligand covalency. The data reveal an increased covalency for the S(Met) relative to N(His) axial ligand and a higher degree of covalency for the ferric states relative to the ferrous states. These results are reproduced by DFT calculations, which are used to evaluate the thermodynamics of the FeS(Met) bond and its dependence on redox state. These results provide insight into a number of previous chemical and physical results on cyt c.

  DOI：

  10.1021/ja5100367

文献信息

• Characterization of singly reduced iron(II) porphyrins
  作者：Robert J. Donohoe、Michael Atamian、David F. Bocian

  DOI：10.1021/ja00253a006

  日期：1987.9

  for all of the complexes reduction results in a low-spin configuration for the metal ion. For (FeTPP)/sup -/ and (FeTPPBr/sub 4/)/sup -/, the unpaired electron resides in the metal d/sub z/sup 2// orbital; however, reduction results in the transfer of a significant amount of paired electron density to the macrocyle through ..pi.. back-bonding. Destabilization the metal d/sub z/sup 2// orbital via ligation

  报告了一系列 Fe/sup II/卟啉的单电子还原产物的光吸收、电子顺磁共振 (EPR) 和共振拉曼 (RR) 光谱。卟啉包括 5,10,15,20-四苯基卟啉 (TPP), 2,7,12,17-tetrabromo-5,10,15,20-四苯基卟啉 (TPPBr/sub 4/), 2,7,12-tricyano -5,10,15,20-四苯基卟啉 (TPP(CN)/sub 3/), 和 2,7,12,17-tetracyano-5,10,15,20-四苯基卟啉 (TPP(CN)/sub 4/ ）。这些卟啉的铁络合物代表一系列，其中还原电位连续地转移到更正的值。RR 和 EPR 数据表明，所有复合物的还原都会导致金属离子的低自旋构型。对于 (FeTPP)/sup -/ 和 (FeTPPBr/sub 4/)/sup -/，未配对电子位于金属 d/sub z/sup 2// 轨道中；然而，减少导致大量成对电子密度通过