⁵⁷Fe(octaethylporphyrin-(2H))(Cl) | 655224-23-0

• 英文名称: ⁵⁷Fe(octaethylporphyrin-(2H))(Cl)
• 英文别名: ⁵⁷Fe(OEP)(Cl)；chloro (57)iron(III)-octaethylporphyrine；(57)Fe(III)(OEP)Cl；[iron(II)octaethylporphyrinate]Cl；[(57)Fe(octaethylporphyrinato)Cl]
• CAS: 655224-23-0
• 化学式: C₃₆H₄₄ClFeN₄
• 分子量: 625.225
• InChiKey: NWWCYXFDLUMYRQ-ZPIGDNBKSA-M

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：

  sodium hydroxide 、 ⁵⁷Fe(octaethylporphyrin-(2H))(Cl) 以 二氯甲烷 、 水 为溶剂， 生成 ((57)Fe(OEP))2O
  参考文献：
  名称：

  八乙基卟啉 Fe(II) 的振动光谱和简正模分析。

  摘要：

  四配位血红素化合物 Fe(II) 八乙基卟啉 Fe(OEP) 的简正模谱是通过将力常数细化为用核共振振动光谱 (NRVS) 测量的实验 Fe 振动态密度来确定的。计算谱与数据的收敛是通过首先在模型结构和力常数上施加 D4 对称性，逐步包括不同的运动内坐标，然后允许 C( i)1 Fe(OEP) 晶体结构。NRVS 改进的简正模与高频拉曼和红外光谱非常一致。对模型卟啉的先验密度泛函理论预测与使用最佳拟合力场计算的核心模式相似，但 D4 和 Ci 模式之间的显着差异强调了卟啉 Fe 正常模式对结构细节的敏感性。Ci 最佳拟合和 NRVS 数据之间的一些差异可归因于正态模式分析中未包括的分子间接触。

  DOI：

  10.1021/jp060345p
• 作为产物：
  描述：

  盐酸 、 iron(III) oxide 、 2,3,7,8,12,13,17,18-octaethyl-21,22-dihydroporphyrin 在 2,4,6-三甲基吡啶 作用下， 以 氯苯 为溶剂， 反应 5.08h， 生成 ⁵⁷Fe(octaethylporphyrin-(2H))(Cl)
  参考文献：
  名称：

  Comprehensive Fe–Ligand Vibration Identification in {FeNO}⁶Hemes

  摘要：

  Oriented single-crystal nuclear resonance vibrational spectroscopy (NRVS) has been used to obtain all iron vibrations in two {FeNO}(6) porphyrinate complexes, five-coordinate [Fe(OEP)(NO)]ClO4 and six-coordinate [Fe(OEP)(2-MeHIm)(NO)]ClO4. A new crystal structure was required for measurements of [Fe(OEP)(2-MeHIm)(NO)]ClO4, and the new structure is reported herein. Single crystals of both complexes were oriented to be either parallel or perpendicular to the porphyrin plane and/or axial imidazole ligand plane. Thus, the FeNO bending and stretching modes can now be unambiguously assigned; the pattern of shifts in frequency as a function of coordination number can also be determined. The pattern is quite distinct from those found for CO or {FeNO}(7) heme species. This is the result of unchanging FeNNO bonding interactions in the {FeNO}(6) species, in distinct contrast to the other diatomic ligand species. DFT calculations were also used to obtain detailed predictions of vibrational modes. Predictions were consistent with the intensity and character found in the experimental spectra. The NRVS data allow the assignment and observation of the challenging to obtain FeIm stretch in six-coordinate heme derivatives. NRVS data for this and related six-coordinate hemes with the diatomic ligands CO, NO, and O-2 reveal a strong correlation between the FeIm stretch and FeNIm bond distance that is detailed for the first time.

  DOI：

  10.1021/ja5105766

文献信息

• Electronic Effects in Transition Metal Porphyrins. 8. The Effect of Porphyrin Substituents, Axial Ligands, "Steric Crowding", Solvent, and Temperature on the 57Fe Chemical Shifts of a Series of Model Heme Complexes
  作者：Larry M. Mink、Jayapal Reddy Polam、Kenner A. Christensen、Michael A. Bruck、F. Ann Walker

  DOI：10.1021/ja00141a027

  日期：1995.9

  screening constant, dpara. Mixed axial ligand complexes where trimethylphosphine is one of the ligands have larger 57Fe chemical shifts when the other ligand (L) is a strong u donortweak JC acceptor, but within a group of closely related ligands such as 4-substituted pyridines, the weakest u donorhtrongest n acceptor ligand produces the largest 57Fe chemical shift (4-CNPy > Py > 4-NMezPy), in line with

  一系列 94.5% 57Fe 富集模型血红素复合物（四苯基卟啉、TPP 及其两种对苯基取代衍生物四甲基卟啉、TMP 和八乙基卟啉、OEP 的复合物）的 57Fe 化学位移，其中三甲基膦作为至少一个通过在适当的 57Fe 频率下使用双共振记录 3iP NMR 光谱来测量轴向配体的 。发现 31P 和 57Fe 化学位移之间的近似相关性使得预测新配合物的 57Fe 化学位移变得容易，从而简化了对适当去耦频率的搜索。取代苯基 TPP 配合物的 57Fe 化学位移随着取代基给电子性质的增加而增加，并且大多数 OEP 配合物的化学位移比它们的 TPP 对应物大 200-250 ppm；这两种趋势都归因于 JC 供体特征的增加，这增加了顺磁屏蔽常数 dpara 的大小。当另一个配体 (L) 是强 u 供体-弱 JC 受体时，其中三甲基膦是配体之一的混合轴向配体复合物具有更大的 57Fe 化学位移，但在一组密切相关的配体（如
• Nuclear Resonance Vibrational Spectroscopy Applied to [Fe(OEP)(NO)]: The Vibrational Assignments of Five-Coordinate Ferrous Heme−Nitrosyls and Implications for Electronic Structure
  作者：Nicolai Lehnert、Mary Grace I. Galinato、Florian Paulat、George B. Richter-Addo、Wolfgang Sturhahn、Nan Xu、Jiyong Zhao

  DOI：10.1021/ic902181e

  日期：2010.5.3

  in the samples of this complex investigated here. The observed porphyrin-based vibrations in the NRVS spectra of 1 are also assigned based on the QCC-NCA results. The obtained force constants of the Fe−NO and N−O bonds are 2.83−2.94 (based on the DFT functional applied) and about 12.15 mdyn/Å, respectively. The electronic structures of 5C ferrous heme−nitrosyls in different model complexes are then

  本研究提供了五坐标 (5C) 亚铁血红素-亚硝酰基络合物 [Fe(OEP)(NO)] ( 1 , OEP 2− = 八乙基卟啉二价阴离子) 和相应的15 N 18 O 的核共振振动光谱 (NRVS) 数据标记复合体。获得的光谱在 522 和 388 cm -1处识别出两个同位素敏感特征，在同位素标记后，它们分别转移到 508 和 381 cm -1。这些特征被分配给 Fe-NO 拉伸 ν(Fe-NO) 和面内 Fe-N-O 弯曲模式 δ ip (Fe-N-O)，后者首次明确分配了1. 使用我们的以量子化学为中心的法向坐标分析 (QCC-NCA) 模拟获得的 NRVS 数据。由于复合物1可能存在于 12 种不同的构象中，涉及 FeNO 和外围乙基取向，因此进行了扩展密度泛函理论 (DFT) 计算和 QCC-NCA 模拟，以确定这些构象如何影响 [Fe(OEP)NO] 的 NRVS 特性. 这些结果表明，FeNO
• Effect of the Sixth Axial Ligand in CS-Ligated Iron(II)octaethylporphyrinates:  Structural and Mössbauer Studies
  作者：Changsheng Cao、S. Dahal、Mayou Shang、Alicia M. Beatty、Wendy Hibbs、Charles E. Schulz、W. Robert Scheidt

  DOI：10.1021/ic030043r

  日期：2003.8.1

  The effect of a sixth ligand in a series of low-spin thiocarbonyl-ligated iron(II)octaethylporphyrinates has been investigated. Six-coordinate complexes have been synthesized and characterized by Mossbauer and infrared spectroscopy and single-crystal X-ray structure determinations. The results are compared with the five-coordinate parent complex. The crystal structures of [Fe(OEP)(CS)(1-MeIm)] and

  已经研究了第六种配体在一系列低旋硫羰基连接的八乙基卟啉铁（II）中的作用。六坐标配合物已经合成，并通过Mossbauer和红外光谱以及单晶X射线结构测定进行了表征。将结果与五坐标父复合体进行比较。报道并讨论了[Fe（OEP）（CS）（1-MeIm）]和[Fe（OEP）（CS）（Py）]的晶体结构。1-甲基咪唑和吡啶衍生物的Fe-C（CS）键距为1.703（4）和1.706（2）A，远比报道的五坐标[Fe（OEP）（CS）的1.662（3）A长。 ）]（Scheidt，WR; Geiger，DK Inorg。Chem。1982，21，1208）。1-甲基咪唑和吡啶配合物的反铁-氮（配体）距离为2.112（3）和2.1550（15）A大约为0。13比类似的双连接的复合物观察到的更长，并且与CS配体的显着结构反式作用一致。Mossbauer对具有几个不同的第六轴向配体的五和六配位硫代羰基衍生物进
• Probing Heme Vibrational Anisotropy: An Imidazole Orientation Effect?
  作者：Qian Peng、Ming Li、Chuanjiang Hu、Jeffrey W. Pavlik、Allen G. Oliver、E. Ercan Alp、Michael Y. Hu、Jiyong Zhao、J. Timothy Sage、W. Robert Scheidt

  DOI：10.1021/ic401644g

  日期：2013.10.7

  The complete iron vibrational spectrum of the five-coordinate high-spin complex [Fe(OEP)(2-MeHIm)], where OEP = octaethylporphyrinato and 2-MeHIM = 2-methylimidazole, has been obtained by oriented single-crystal nuclear resonance vibrational spectroscopy (NRVS) data. Measurements have been made in three orthogonal directions, which provides quantitative information for all iron motion. These experimental data, buttressed by density functional theory (DFT) calculations, have been used to define the effects of the axial ligand orientation. Although the axial imidazole removes the degeneracy in the in-plane vibrations, the imidazole orientation does not appear to control the direction of the in-plane iron motion. This is in contrast to the effect of the imidazolate ligand, as defined by DFT calculations, which does have substantial effects on the direction of the in-plane iron motion. The axial NO ligand has been found to have the strongest orientational effect (Angew. Chem., Int. Ed., 2010, 49, 4400). Thus the strength of the directional properties are in the order NO > imidazolate > imidazole, consistent with the varying strength of the Fe-ligand bond.