chloroiron(III)tetramethylchiroporphyrin | 199784-29-7

• 英文名称: chloroiron(III)tetramethylchiroporphyrin
• 英文别名: FeCl(tetramethylchiroporphyrin)
• CAS: 199784-29-7
• 化学式: C₄₈H₅₂ClFeN₄O₈
• 分子量: 904.263
• InChiKey: MYLOHVDJVXKIMM-PNXOXAAXSA-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：

  chloroiron(III)tetramethylchiroporphyrin 在 Al₂O₃ 作用下， 以 苯 为溶剂， 生成 Fe(OH)(tetramethylchiroporphyrin)
  参考文献：
  名称：

  High-Spin Iron(III) Tetramethylchiroporphyrins:  Structural, Magnetic, and ¹H NMR Studies

  摘要：

  The chloroiron(III) complex of alpha beta alpha beta-tetramethylchiroporphyrin: FeCl(TMCP), was prepared, and its structure was determined by X-ray crystallography. Black crystals of FeCl(TMCP). 0.72CH(2)Cl(2) form in the tetragonal space group P4(3)2(1)2 with a = b = 13.245(1) Angstrom and c = 26.355(5) Angstrom at 130 K with Z = 4. The structure shows an unusual five-coordinate high-spin iron(III) center in a strongly ruffled and domed porphyrin, with short equatorial bond distances (Fe-N(av) 2.034(9) Angstrom), and the iron 0.64 Angstrom out of the porphyrin mean plane toward the chlorine atom. The solid-state magnetic moment is 5.92 mu(B) at 20 K, slightly decreasing to 5.68 mu(B) at 300 K. In solution FeCl(TMCP) can be easily transformed to FeBr(TMCP) or FeOH(TMCP). The H-1 NMR spectra of the three species are consistent with their C-2 symmetry and S = (5)/(2) spin state. The pyrroIe proton resonances are shifted downfield to 80-100 ppm at 293 K, more than in the corresponding tetraaryl derivatives. The cyclopropyl protons on C-1, alpha to the porphyrin meso position, appear at ca. 160-200 ppm, in keeping with the nearly perpendicular orientation of the C-1-H bond with respect to the porphyrin mean plane. The temperature dependence of the IH NMR spectrum of FeCl(TMCP) suggests substantial zero-field splitting.

  DOI：

  10.1021/ic9711933
• 作为产物：
  描述：

  tetramethylchiroporphyrin 、 iron(II) chloride 以 乙醇 、 氯仿 为溶剂， 以70%的产率得到chloroiron(III)tetramethylchiroporphyrin
  参考文献：
  名称：

  High-Spin Iron(III) Tetramethylchiroporphyrins:  Structural, Magnetic, and ¹H NMR Studies

  摘要：

  The chloroiron(III) complex of alpha beta alpha beta-tetramethylchiroporphyrin: FeCl(TMCP), was prepared, and its structure was determined by X-ray crystallography. Black crystals of FeCl(TMCP). 0.72CH(2)Cl(2) form in the tetragonal space group P4(3)2(1)2 with a = b = 13.245(1) Angstrom and c = 26.355(5) Angstrom at 130 K with Z = 4. The structure shows an unusual five-coordinate high-spin iron(III) center in a strongly ruffled and domed porphyrin, with short equatorial bond distances (Fe-N(av) 2.034(9) Angstrom), and the iron 0.64 Angstrom out of the porphyrin mean plane toward the chlorine atom. The solid-state magnetic moment is 5.92 mu(B) at 20 K, slightly decreasing to 5.68 mu(B) at 300 K. In solution FeCl(TMCP) can be easily transformed to FeBr(TMCP) or FeOH(TMCP). The H-1 NMR spectra of the three species are consistent with their C-2 symmetry and S = (5)/(2) spin state. The pyrroIe proton resonances are shifted downfield to 80-100 ppm at 293 K, more than in the corresponding tetraaryl derivatives. The cyclopropyl protons on C-1, alpha to the porphyrin meso position, appear at ca. 160-200 ppm, in keeping with the nearly perpendicular orientation of the C-1-H bond with respect to the porphyrin mean plane. The temperature dependence of the IH NMR spectrum of FeCl(TMCP) suggests substantial zero-field splitting.

  DOI：

  10.1021/ic9711933

文献信息

• An Integrated Approach to the Mid-Spin State (<i>S</i> = 3/2) in Six-Coordinate Iron(III) Chiroporphyrins
  作者：Jean-Pierre Simonato、Jacques Pécaut、Laurent Le Pape、Jean-Louis Oddou、Claudine Jeandey、Maoyu Shang、W. Robert Scheidt、Jacek Wojaczyński、Stanisław Wołowiec、Lechosław Latos-Grażyński、Jean-Claude Marchon

  DOI：10.1021/ic000150a

  日期：2000.9.1

  An intermediate-spin state very close to the mid-spin state (S = 3/2) can be stabilized in a ferric porphyrin by an integrated approach which combines the favorable effects of a weak axial field strength and of a small macrocycle hole. Axial ligand exchange by reaction of chloroiron(III)tetramethylchiroporphyrin [(TMCP)FeCl] with silver perchlorate in ethanol-chloroform leads to ethanol-ligated ferric

  通过结合了弱轴向磁场强度和小大环孔的有利作用的集成方法，可以在铁卟啉中稳定非常接近中间自旋态的中间自旋态（S = 3/2）。在乙醇-氯仿中通过亚铁（III）四甲基手性卟啉[（TMCP）FeCl]与高氯酸银反应的轴向配体交换导致乙醇连接的铁手性卟啉。含有双乙醇配合物[[（TMCP）FeIII（EtOH）2] ClO4]和混合乙醇-水配合物[[（TMCP）FeIII（EtOH）（H2O）] ClO4]的三种变体的两种不同的结晶产物已在结构上进行了表征在固态。褶皱的卟啉的小孔和弱的轴向氧连接导致强烈四边形扭曲的配合物。六坐标物种显示出长的轴向Fe-O键距离（2。173（5）-2.272（4）A）和在铁卟啉中发现的最短赤道Fe-N（av）距离（1.950（5）-1.978（7）A），反映了一个单独占据的dz2轨道和一个dx2-y2轨道大量减少。在两个晶体学上独立的混合乙醇-水物种中，轴向Fe-O键