(octaethylporphinato)iron(III) methoxide | 50652-07-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: (octaethylporphinato)iron(III) methoxide
• 英文别名: [Fe(octaethylporphyrin)(OMe)]；[Fe(OEP)(OMe)]；[Fe(III)(octaethylporphinato)(OMe)]
• CAS: 50652-07-8
• 化学式: C₃₇H₄₇FeN₄O
• 分子量: 619.653
• InChiKey: ZRFGXIXBIDMQRL-YAJYDHHFSA-N

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：
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• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (octaethylporphinato)iron(III) methoxide 在 苯酚 作用下， 以 二氯甲烷 为溶剂， 生成 (octaethylporphyrinato)Fe(III)OC6H5
  参考文献：
  名称：

  Uno, Tadayuki; Hatano, Keiichiro; Nishimura, Yoshifumi, Inorganic Chemistry, 1990, vol. 29, # 15, p. 2803 - 2807

  摘要：

  DOI：
• 作为产物：
  描述：

  iron(III)octaethylporphyrin chloride 在 KOH 、 CH₃OH 作用下， 以 氯仿 、 水 为溶剂， 生成 (octaethylporphinato)iron(III) methoxide
  参考文献：
  名称：

  (Methoxo)(八乙基卟啉)铁(III)的制备及分子结构

  摘要：

  报道了 Fe(OEP)(OMe) 的 X 射线结构：Fe(C36H44N4)(CH3O)，FW=619.7，单斜晶系，P21/c，a=13.412(5)A，c=18.912(8)A， β=106.28(3)°，V=3348(4) A3，Z=4。揭示了在固态下具有 π-π 二聚卟啉相互作用的甲醇配位铁 (III) 卟啉酸盐。简要讨论了甲醇盐的容易形成。

  DOI：

  10.1246/bcsj.63.1825

文献信息

• Synthesis and molecular structures of S-2-FcNHCOC6H4SH and [MIII(OEP)(S-2-FcNHCOC6H4)] (Fc = ferrocenyl, M = Fe, Ga): Electrochemical contributions of intramolecular SH⋯O C and NH⋯S hydrogen bonds
  作者：Taka-aki Okamura、Taku Iwamura、Hitoshi Yamamoto、Norikazu Ueyama

  DOI：10.1016/j.jorganchem.2006.08.067

  日期：2007.1

  and its porphyrin-thiolate compounds, [MIII(OEP)(S-2-FcNHCOC6H4)] (M = Fe (2a), Ga (3a)) were synthesized and characterized by X-ray analysis, spectroscopic and electrochemical measurements. The corresponding 4-substituted derivatives (1b–3b) were also synthesized to estimate the contribution of substituent effects. The formation of intramolecular SH⋯OC or NH⋯S hydrogen bonds in solution was established

  具有二茂铁部分的新型氧化还原活性硫醇盐配体S-2-FcNHCOC 6 H 4 SH（1a）及其卟啉硫醇盐化合物[M III（OEP）（S-2-FcNHCOC 6 H 4）]（ M = Fe（2a），Ga（3a））合成并通过X射线分析，光谱和电化学测量进行表征。相应的4-取代的衍生物（1b – 3b）也被合成以估计取代基效应的贡献。溶液中分子内SH⋯OC或NH⋯S氢键的形成由1确定1 H NMR和IR光谱。发现氢键和π共轭对Fc和铁-卟啉部分的氧化还原电势的协同作用。
• Characterization of the Bridged Hyponitrite Complex {[Fe(OEP)]₂(μ-N₂O₂)}: Reactivity of Hyponitrite Complexes and Biological Relevance
  作者：Timothy C. Berto、Nan Xu、Se Ryeon Lee、Anne J. McNeil、E. Ercan Alp、Jiyong Zhao、George B. Richter-Addo、Nicolai Lehnert

  DOI：10.1021/ic5002573

  日期：2014.7.7

  assess potential reaction intermediates. In particular, there have been many proposed mechanisms that invoke the formation of a hyponitrite bridge between the heme b3 and nonheme iron (FeB) centers within the NorBC active site. However, the reactivity of bridged iron hyponitrite complexes has not been investigated much in the literature. The model complex [Fe(OEP)]2(μ-N2O2)} offers a unique opportunity

  细菌NO还原酶（NorBC）对一氧化氮（NO）的解毒代表了NO如何在细胞中进行厌氧解毒的范例。为了阐明这种酶的机理，模型复合物提供了一种方便的方法来评估潜在的反应中间体。特别地，已经提出了许多机制，该机制引起在NorBC活性位点内血红素b 3和非血红素铁（Fe B）中心之间形成亚硝酸盐桥。然而，在文献中没有对桥连的亚铁盐亚铁配合物的反应性进行太多研究。该模型复杂[铁（OEP）] 2（μ-N 2 ö 2）}提供了一个独特的机会来研究这种亚硝酸盐桥联的复合物的电子结构和反应性。这里，我们报告的[铁（OEP）]的详细表征2（μ-N 2 ö 2使用IR，核共振振动光谱学，电子顺磁共振，并用SQUID磁力沿磁圆二色光谱的组合）}。这些结果表明，该复合物的基态电子结构最好是作为具有两个中间-自旋（描述小号= 3 / 2），这些弱反铁磁跨越所述N个耦合铁中心2 ö 2 2-桥。类似的复合物[Fe（PPDME）]2（μ-N
• Uno, Tadayuki; Hatano, Keiichiro; Nawa, Tatsuya, Inorganic Chemistry, 1991, vol. 30, # 23, p. 4322 - 4327
  作者：Uno, Tadayuki、Hatano, Keiichiro、Nawa, Tatsuya、Nakamura, Kazuko、Nishimura, Yoshifumi、Arata, Yoji

  DOI：——

  日期：——
• 2-Methylimidazole Does Not Bind to (Octaethylporphinato)iron(III) Chloride in the Presence of Methanol: A Resonance Raman Study
  作者：Tadayuki Uno、Keiichiro Hatano、Yoshifumi Nishimura

  DOI：10.1021/ja00088a068

  日期：1994.5
• Synthesis and Electron Delocalization of [Fe4S4]-S-Fe(III) Bridged Assemblies Related to the Exchange-Coupled Catalytic Site of Sulfite Reductases
  作者：Lisheng Cai、R. H. Holm

  DOI：10.1021/ja00095a021

  日期：1994.8

  Because of the pervasive occurrence of magnetically coupled siroheme and Fe4S4 units in assimilatory and dissimilatory sulfite and nitrite reductases, we have undertaken the synthesis of the sulfide-bridged assembly Fe4S4-S-heme as a possible analogue to the active sites of certain assimilatory enzymes. The approach has utilized iron subsite-differentiated clusters of the type [Fe4S4(LS(3))L'](2-), which undergo regiospecific substitution at the unique subsite. Reaction of [Fe4S4(LS(3))(SEt)](2-) with limited H2S in acetonitrile affords the functionalized cluster [Fe4S4(LS(3))(SH)](2-) (4), which exists in equilibrium with the mu-S double cubane [Fe4S4(LS(3))]S-2}(4-) (6) and H2S. Reaction of 4 and [Fe(salen)]O-2 gave the bridged assembly [Fe4S4(LS(3))-S-Fe-III(salen)](2-) (8), detectable by its characteristic isotropically shifted H-1 NMR spectrum. Six routes were devised to a related heme-based assembly: directed acid-base coupling of 4 with [Fe(OEP)]O-2, [Fe(OEP)(OMe)], [Fe(OEP)(OC(Me)=CH2)], and [Fe(OEP)(OClO3)]/Et(3)N; Si-S bond cleavage in the reaction of [Fe4S4(LS(3))(SSiEt(3))](2-) with [Fe(OEP)F]; oxidative addition of [Fe-II(OEP)] to the disulfide bond of the mu-S-2 double cubane [Fe4S4(LS(3))]S-2(2)}(4-) (7). In each case, the product was [Fe4S4(LS(3))-S-Fe-III(OEP)](2-) (9), recognizable by UV-visible absorption and H-1 NMR spectra. Both 8 and 9 contain [Fe4S4](2+) and high-spin Fe(III) fragments. Isotropic shifts mainly contact in origin that are enhanced by factors of 7-12 compared to those of precursor cluster 4, and the Curie-type temperature dependence of the shifts of 9, originate from extensive spin localization from the Fe(III) fragment to the cluster. This effect requires the existence of a covalent bridge between the fragments and, together with the methods of synthesis and other spectroscopic observations, provides structure proof of the bridged assemblies. These species sustain two one-electron reduction reactions; other reactions of 9, which alter or cleave the bridge, are summarized. The electronic features of bridged assemblies such as 8 and 9 approach the intrinsic magnetic and spectroscopic properties of a structurally similar unit in the oxidized enzymes and potentially provide a means of identification of such units. (LS(3) = 1,3,5-tris[(4,6-dimethyl-3-mercaptophenyl)-thio]-2,4,6-tris(p-tolylthio)benzene(3-); OEP octaethylporphyrinate(2-); salen = 1,2-bis(salicylidenearnino)ethane-(2-).)