(2,3,7,8,12,13,17,18-octaethylporphinato)manganese(III) acetate | 28109-84-4

• 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: (2,3,7,8,12,13,17,18-octaethylporphinato)manganese(III) acetate
• 英文别名: (2,3,7,8,12,13,17,18-octaethylporphynato)acetatomanganese(III)；(acetato)(octaethylporphinato)manganese(III)；(acetato)Mn(III)(octaethylporphyrin)；(AcO)Mn(octaethylporphine-2H)；Mn(OAc)(octaethylporphyrin)；(AcO)Mn(OEP)
• CAS: 28109-84-4
• 化学式: C₃₈H₄₇MnN₄O₂
• 分子量: 646.755
• InChiKey: YLKDBKHQTPCXCS-YAJYDHHFSA-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：

  (2,3,7,8,12,13,17,18-octaethylporphinato)manganese(III) acetate 、 sodium thiocyanide 以 水 、 N,N-二甲基甲酰胺 为溶剂， 生成 (thiocyanato)(octaethylporphinato)manganese(III)
  参考文献：
  名称：

  Disproportionation of hydrogen peroxide in the presence of Mn(III) complexes with various porphyrins and acid anions

  摘要：

  The kinetics of homogeneous decomposition of H2O2 in the presence of Mn(IIII) complexes with octaethylporphine or meso-phenyloctaethylporphines and acid anions Cl-, AcO-, and SCN- was studied by volumetry. The ionic-molecular mechanism of the transformation, involving reversible coordination of the H2O2 molecule, its irreversible decomposition with the release of H2O and removal of two electrons from the metal porphyrin, reversible coordination of the second peroxide molecule in the form of HO2-, and slow irreversible reduction of the catalyst with the release of O-2 and H2O was substantiated by electronic absorption spectra. The catalytic activity of Mn(III) porphyrin complexes is independent of the acid anion present as extra ligand, but depends on the structure of the porphyrin ligand, which can be used for controlling the catalytic activity. Unsymmetrical (chloro)(monophenyloctaethylporphinato)manganese(III) is the most active; it increases the rate of O-2 evolution by a factor of 2 at the peroxide : catalyst molar ratio of (3 x 10(5)):1.

  DOI：

  10.1134/s1070363206090210
• 作为产物：
  描述：

  2,3,7,8,12,13,17,18-octaethylporphyrin 、 manganese (II) acetate tetrahydrate 以 not given 为溶剂， 生成 (2,3,7,8,12,13,17,18-octaethylporphinato)manganese(III) acetate
  参考文献：
  名称：

  Disproportionation of hydrogen peroxide in the presence of Mn(III) complexes with various porphyrins and acid anions

  摘要：

  The kinetics of homogeneous decomposition of H2O2 in the presence of Mn(IIII) complexes with octaethylporphine or meso-phenyloctaethylporphines and acid anions Cl-, AcO-, and SCN- was studied by volumetry. The ionic-molecular mechanism of the transformation, involving reversible coordination of the H2O2 molecule, its irreversible decomposition with the release of H2O and removal of two electrons from the metal porphyrin, reversible coordination of the second peroxide molecule in the form of HO2-, and slow irreversible reduction of the catalyst with the release of O-2 and H2O was substantiated by electronic absorption spectra. The catalytic activity of Mn(III) porphyrin complexes is independent of the acid anion present as extra ligand, but depends on the structure of the porphyrin ligand, which can be used for controlling the catalytic activity. Unsymmetrical (chloro)(monophenyloctaethylporphinato)manganese(III) is the most active; it increases the rate of O-2 evolution by a factor of 2 at the peroxide : catalyst molar ratio of (3 x 10(5)):1.

  DOI：

  10.1134/s1070363206090210
• 作为试剂：
  描述：

  双氧水 在 (2,3,7,8,12,13,17,18-octaethylporphinato)manganese(III) acetate 氢氧化钾 作用下， 以 水 、 N,N-二甲基甲酰胺 为溶剂， 生成 氧气
  参考文献：
  名称：

  Disproportionation of hydrogen peroxide in the presence of Mn(III) complexes with various porphyrins and acid anions

  摘要：

  The kinetics of homogeneous decomposition of H2O2 in the presence of Mn(IIII) complexes with octaethylporphine or meso-phenyloctaethylporphines and acid anions Cl-, AcO-, and SCN- was studied by volumetry. The ionic-molecular mechanism of the transformation, involving reversible coordination of the H2O2 molecule, its irreversible decomposition with the release of H2O and removal of two electrons from the metal porphyrin, reversible coordination of the second peroxide molecule in the form of HO2-, and slow irreversible reduction of the catalyst with the release of O-2 and H2O was substantiated by electronic absorption spectra. The catalytic activity of Mn(III) porphyrin complexes is independent of the acid anion present as extra ligand, but depends on the structure of the porphyrin ligand, which can be used for controlling the catalytic activity. Unsymmetrical (chloro)(monophenyloctaethylporphinato)manganese(III) is the most active; it increases the rate of O-2 evolution by a factor of 2 at the peroxide : catalyst molar ratio of (3 x 10(5)):1.

  DOI：

  10.1134/s1070363206090210

文献信息

• Resonance Raman and infrared spectra of azidoiron(III) and azidomanganese(III) porphyrins
  作者：Roman S. Czernuszewicz、Wolf-Dieter Wagner、Gigi B. Ray、Kazuo Nakamoto

  DOI：10.1016/0022-2860(91)87130-a

  日期：1991.1

  Abstract Infrared and resonance Raman (RR) frequencies of ligand modes have been measured for a series of five-coordinate azidoiron(III) and azidomanganese (III) porphyrins and their 15N3,15N14N2 (Fe, Mn) and 54Fe (Fe) isotopically-substituted analogues. The RR spectra of Fe porphyrins are dominated by the ν(Fe-N3) stretching mode (≈420 cm−1) when excitation is made in resonance with porphyrin π−π*

  摘要 已经测量了一系列五配位叠氮铁 (III) 和叠氮锰 (III) 卟啉及其 15N3,15N14N2 (Fe, Mn) 和 54Fe (Fe) 同位素取代的配体模式的红外和共振拉曼 (RR) 频率。类似物。当与卟啉 π−π* 跃迁 (406.7−514.5 nm) 共振激发时，Fe 卟啉的 RR 光谱由 ν(Fe-N3) 拉伸模式 (≈420 cm−1) 支配。相比之下，λ(N3) 弯曲 (≈630 cm-1) 和 νas (N3) 不对称拉伸 (≈2040 cm-1) 模式是叠氮-Mn 卟啉的 RR 光谱中发生的唯一配体振动。这两种模式通过分离的 Soret 带之间的可见激发得到增强，表明该区域存在涉及叠氮化物 π 电子的新电荷转移跃迁。这些波段的极化性质 (ϱ=0. 25) 暗示结合的 N3 配体的有效对称性是 Cs。N3Mn(III) TMP（TMP=四甲基卟啉）的 IR 光谱中
• Pyridine coordination to manganese(III) porphyrins: The effect of multiple functional substitution in porphyrin
  作者：E. N. Ovchenkova、M. E. Klyueva、T. N. Lomova

  DOI：10.1134/s0036023617110134

  日期：2017.11

  To synthesize donor-acceptor complexes exhibiting biological activity, the reaction of (2,3,7,8,12,13,17,18-octaalkylporphinato)manganese(III) containing axial acetate and chloride ions with pyridine has been quantitatively studied. In all cases, equilibrium is established instantaneously to give 1 : 1 donor-acceptor complexes. The key spectral characteristics and stability parameters have been obtained for donor-acceptor dyads. Multiple functional substitution of the porphyrin macroheterocycle can be used to control the properties of porphyrins and dyads based on them.
• ——
  作者：E. M. Kuvshinova、D. L. Kuz'min、S. G. Pukhovskaya、A. S. Semeikin、O. A. Golubchikov

  DOI：10.1023/a:1025673427341

  日期：——

  Octaethyl-, 5-phenyloctaethyl-, 5,15-diphenyloctaethyl-, 5,10,15,20-tetraphenyloctaethyl, and dodecaphenylporphyrins were prepared, and their geometries were optimized by the method of molecular mechanics. The deformation of the porphyrin macroring grows as the number of phenyl groups is increased. The dissociation kinetics of the manganese, cobalt, and copper complexes of the porphyrins in solutions of sulfuric acid in acetic acid were studied. The kinetic parameters of the dissociation of metal porphyrins were analyzed in relation to the porphyrin structure and nature of the metal.
• Keith Woo; Goll, James G.; Czapla, Donald J., Journal of the American Chemical Society, 1991, vol. 113, # 22, p. 8478 - 8484
  作者：Keith Woo、Goll, James G.、Czapla, Donald J.、Alan Hays

  DOI：——

  日期：——