{Fe(octaethyloxophlorinate)}2 | 148442-42-6

• 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: {Fe(octaethyloxophlorinate)}2
• 英文别名: [Fe(III)(octaethyloxophlorin trianion)]2；[Fe(octaethyloxophlorin(3-))]2；Fe2(octaethyloxophlorinato)2；(Fe(III)(OEPO))2；Fe2(OEPO)2
• CAS: 148442-42-6
• 化学式: C₇₂H₈₆Fe₂N₈O₂
• 分子量: 1207.22
• InChiKey: KJMCAIUHSJGEMG-CCTKZQMWSA-L

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(octaethyloxophlorinate)}2 在 Br₂ 作用下， 以 氯仿 为溶剂， 以93%的产率得到
  参考文献：
  名称：

  铁氧磷的化学。2. 氧化铁 (III) 八乙基氧代绿素二聚体和逐步观察氧代绿素大环的双电子氧化

  摘要：

  已经研究了铁氧代叶绿素（内消旋羟基卟啉）复合物的氧化，以了解可能有助于血红素加氧酶催化的血红素破坏的基本化学反应。铁 (III) 八乙基氧代血红素二聚体 [Fe III (OEPO)] 2 与分子溴的反应导致形成两种新的高度氧化的配合物，BrFe III (OEPO . ) 和 Br 2 Fe III (OEPOx)（其中 OEPO .和 OEPOx 分别是八乙基氧杂绿素二阴离子自由基和氧化的八乙基氧杂绿素单阴离子​​），其中实验数据表明，氧化的是配体而不是铁

  DOI：

  10.1021/ja00078a024
• 作为产物：
  描述：

  iron(III)octaethylporphyrin chloride 在 potassium cyanide 、 air 、 维生素 C 作用下， 以 甲醇 为溶剂， 以87.7%的产率得到{Fe(octaethyloxophlorinate)}2
  参考文献：
  名称：

  Coupled Oxidation of Heme without Pyridine. Formation of Cyano Complexes of Iron Oxophlorin and 5-Oxaporphyrin (Verdoheme) from Octaethylheme

  摘要：

  Oxidative degradation of iron porphyrins under coupled oxidation conditions, which generally has involved pyridine as solvent and source of axial Ligands, results in the production of verdoheme, the iron complex of 5-oxaporphyrin in which an oxygen atom replaces a methine,group. Under pyridine-free conditions, ClFeIII(OEP) (OEP is the dianion of octaethylporphyrin) and {Fe-III(OEPO)}(2) (OEPO is the trianion of octaethyloxophlorin) have been converted into the 5-oxaporphyrin complex (verdoheme) {(NC)(2)Fe-III(OEOP)} (OEOP is the anion of octaethyl-5-oxaporphyrin). Additionally, through control of;the cyanide ion concentration, the:oxidation of ClFeIII(OEP) can be stopped to produce {Fe-III(OEPO)}2 or allowed to proceed to give {(NC)(2)Fe-III(OEOP)}. A convenient method for the preparation of {Fe-III(OEPO)}(2), and from it the free base H2OEPOH, is reported. Anionic complexes, [(NC)(py)Fe(OEPO)](-) and [(NC)(2)Fe(OEPO)](2-), related to these oxidative degradation processes have been obtained through the addition of bis(triphenylphosphine)iminium cyanide to (py)(2)Fe(OEPO) in pyridine solution or through cleavage of {Fe-III(OEPO)}(2) with potassium cyanide in methanol or with tetra(n-butyl)ammonium cyanide in chloroform solution. The products have been characterized principally through their characteristic H-1 NMR spectra, which show sizable hyperfine shifts with meso resonances upfield and methylene resonances with both up-and downfield shifts. in the presence of air, [(NC)(2)Fe(OEPO)](2-) undergoes oxidation to form the 5-oxaporphyrin complex (verdoheme) {(NC)(2)Fe-III(OEOP)}. Treatment of BrFeIII(OEPO .) with CN- produces [(NC)(2)Fe(OEPO)](-), which can also be obtained through oxidation of [(NC)(2)Fe(OEPO)](2-) with diiodine.

  DOI：

  10.1021/ic970503e

文献信息

• Reactions of <i>meso</i>-Hydroxyhemes with Carbon Monoxide and Reducing Agents in Search of the Elusive Species Responsible for the <i>g</i> = 2.006 Resonance of Carbon Monoxide-Treated Heme Oxygenase. Isolation of Diamagnetic Iron(II) Complexes of Octaethyl-<i>m</i><i>eso</i>-hydroxyporphyrin
  作者：Sankar Prasad Rath、Marilyn M. Olmstead、Alan L. Balch

  DOI：10.1021/ic049581+

  日期：2004.10.1

  16 h period. Although a resonance at g = 2.006 was observed in the EPR spectrum of the sample during the reaction, the isolated product is EPR silent. The spectroscopic features of the final solution are identical to those of a solution formed by treating (py)(2)Fe(II)(OEPOH) with carbon monoxide. Addition of hydrazine to solutions of (OC)(py)Fe(II)(OEPOH) produces red, diamagnetic (OC)(N(2)H(4))Fe(II)(OEPOH)

  为了检查当用Fe处理Fe（III）状态的羟基化血红素-血红素加氧酶复合物时g = 2.006共振的可能模型，CO和还原剂与（py）（2）Fe（III）（ OEPO）和[Fe（III）（OEPO）]（2）（OEPO是八乙基-间位-羟基卟啉的三阴离子）已经过检验。（py）（2）Fe（III）（OEPO）的吡啶溶液在无二氧的二氮气氛下与锌汞齐（或肼）在几分钟内反应生成亮红色的（py）（2） Fe（II）（OEPOH）.2py.0.33H（2）O，已以结晶形式分离。吡啶-d（5）溶液中（py）（2）Fe（II）（OEPOH）的（1）H NMR光谱表明存在反磁性化合物，并且未观察到该化合物的EPR共振。用一氧化碳处理吡啶-d（5）中的（py）（2）Fe（II）（OEPOH）溶液会在暴露30 s后产生光谱变化，表明形成了反磁性（OC）（py） Fe（II）（OEPOH）。用一氧化碳处理（py）（2）F
• Electron Distribution in Iron Octaethyloxophlorin Complexes. Importance of the Fe(III) Oxophlorin Trianion Form in the Bis-pyridine and Bis-imidazole Complexes
  作者：Sankar Prasad Rath、Marilyn M. Olmstead、Alan L. Balch

  DOI：10.1021/ic0607033

  日期：2006.7.1

  (Im)2Fe(III)(OEPO).2THF, and (Im)2Fe(III)(OEPO).1.6CHCl3 have been examined by single-crystal X-ray diffraction, measurement of magnetic moments as a function of temperature, and EPR and NMR spectral studies. The results clearly show that both complexes exist in the Fe(III)/oxophlorin trianion form rather than the Fe(II)/oxophlorin radical form previously established for (2,6-xylylNC)(2)Fe(II)(OEPO.)

  在八乙基氧代卟啉（H3OEPO）络合物中，铁与卟啉大环之间的电子分配一直是一个令人困扰的问题。特别是对于（Py）2Fe（OEPO），它是血红素降解的重要中间体，已经考虑了分别涉及Fe（III），Fe（II）或Fe（I）的三个共振结构。为了澄清这个问题，（Py）2Fe（III）（OEPO），（Im）2Fe（III）（OEPO）.2THF和（Im）2Fe（III）（OEPO）.1.6CHCl3的电子和几何结构具有通过单晶X射线衍射，磁矩作为温度的函数的测量以及EPR和NMR光谱研究对这些元素进行了研究。结果清楚地表明，两种络合物均以Fe（III）/氧代卟啉三价阴离子形式存在，而不是先前为（2,6-xylylNC）（2）Fe（II）（OEPO。）建立的Fe（II）/氧代菲林自由基形式存在。 。在10至300 K的固态下，（Py）2Fe（III）（OEPO）以高自旋（S = 5/2）状态存在，轴向配体位于平行平面，平面卟啉和长轴向Fe
• Balch, Alan L.; Latos-Grazyński, Lechosław; Noll, Bruce C., Inorganic Chemistry, 1992, vol. 31, # 11, p. 2248 - 2255
  作者：Balch, Alan L.、Latos-Grazyński, Lechosław、Noll, Bruce C.、Olmstead, Marilyn M.、Zovinka, Edward P.

  DOI：——

  日期：——
• The Effects of Axial Ligands on Electron Distribution and Spin States in Iron Complexes of Octaethyloxophlorin, Intermediates in Heme Degradation
  作者：Sankar Prasad Rath、Marilyn M. Olmstead、Alan L. Balch

  DOI：10.1021/ja0316014

  日期：2004.5.1

  The results presented here show that the nature of the axial ligand can alter the distribution of electrons between the metal and the porphyrin in complexes where there is an oxygen atom replacing one of the meso protons. The complexes (1-MeIM)(2)Fe-III(OEPO) and (2,6-xylyINC)(2)Fe-II(OEPO.) (where OEPO is the trianionic octaethyloxophlorin ligand and OEPO. is the dianionic octaethyloxophlorin radical) were prepared by addition of an excess of the appropriate axial ligand to a slurry of Fe-III(OEPO)}(2) in chloroform under anaerobic conditions. The magnetic moment of (2,6-xylylNC)(2)Fe-II(OEPO.) is temperature invariant and consistent with a simple S = (1)/(2) ground state. This complex with an EPR resonance at g = 2.004 may be considered as a model for the free-radical like EPR signal seen when the meso-hydroxylated heme/ heme oxygenase complex is treated with carbon monoxide. In contrast, the magnetic moment of (1-MelM)(2)Fe-III(OEPO) drops with temperature and indicates a spin-state change from an S = (5)/(2) or an admixed S = (3)/(2),(5)/(2) state at high temperatures (near room temperature) to an S = 1/2 state at temperatures below 100 K. X-ray diffraction studies show that each complex crystallizes in centrosymmetric form with the expected six-coordinate geometry. The structure of (1-Melm)(2)Fe-III(OEPO) has been determined at 90, 129, and 296 K and shows a gradual and selective lengthening of the Fe-N(axial bond). This behavior is consistent with population of a higher spin state at elevated temperatures.
• Balch, Alan L.; Latos-Grazyński, Lechosław; St. Claire, Tamara N., Inorganic Chemistry, 1995, vol. 34, # 6, p. 1395 - 1401
  作者：Balch, Alan L.、Latos-Grazyński, Lechosław、St. Claire, Tamara N.

  DOI：——

  日期：——