(5,15-[2,5-bis(2'-phenyleneoxymethyl)-1,4-dimethoxybenzene]-3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporphyrinato)zinc(II) | 354575-84-1

• 分子结构分类: 有机化合物
• 英文名称: (5,15-[2,5-bis(2'-phenyleneoxymethyl)-1,4-dimethoxybenzene]-3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporphyrinato)zinc(II)
• 英文别名: zinc 5,15-[2,5-bis(2'-phenylenoxymethylene)-2,5-dimethoxy-p-phenylene]-2,8,12,18-tetrabutyl-3,7,13,17-tetramethylporphyrin
• CAS: 354575-84-1
• 化学式: C₆₂H₇₀N₄O₄Zn
• 分子量: 1000.65
• InChiKey: OYLLWMHZWNYPQC-SPIXISCGSA-N

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：

  咪唑 、 (5,15-[2,5-bis(2'-phenyleneoxymethyl)-1,4-dimethoxybenzene]-3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporphyrinato)zinc(II) 以 邻二甲苯 为溶剂， 生成 (imidazole)Zn(5,15-[2,5-bis(2'-phenyleneoxymethyl)-1,4-dimethoxybenzene]-3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporphyrinato)
  参考文献：
  名称：

  Kinetics of Oxidation of “Capped” Zinc Porphyrin Containing a 2,5-Dimethoxyphenylene “Cap” with Organic Peroxides in the Presence of Imidazole

  摘要：

  5,15-[2,5- 双（2′-亚苯基氧甲基）-1,4-二甲氧基苯]-2,8,12,18-四甲基-3,7,13,17-四丁基卟啉的锌 "封端 "络合物在 298 K 下与有机过氧化物发生氧化反应，导致络合物完全分解。氮基对金属卟啉的氧化速率有显著影响。确定了反应的动力学参数。通过 PM3 计算，优化了立体应变金属卟啉及其氧化中间产物的结构。几何分析表明，在形成额外络合物并与过氧化物反应时，大孔的变形会增加。

  DOI：

  10.1007/s11176-005-0321-z
• 作为产物：
  描述：

  blocked 5,15-[2,5-bis(2'-phenylenoxymethylene)-2,5-dimethoxy-p-phenylene]-2,8,12,18-tetrabutyl-3,7,13,17-tetramethylporphyrin 、 zinc diacetate 以 苯 为溶剂， 以95%的产率得到(5,15-[2,5-bis(2'-phenyleneoxymethyl)-1,4-dimethoxybenzene]-3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporphyrinato)zinc(II)
  参考文献：
  名称：

  Kinetics of Oxidation of “Capped” Zinc Porphyrin Containing a 2,5-Dimethoxyphenylene “Cap” with Organic Peroxides in the Presence of Imidazole

  摘要：

  5,15-[2,5- 双（2′-亚苯基氧甲基）-1,4-二甲氧基苯]-2,8,12,18-四甲基-3,7,13,17-四丁基卟啉的锌 "封端 "络合物在 298 K 下与有机过氧化物发生氧化反应，导致络合物完全分解。氮基对金属卟啉的氧化速率有显著影响。确定了反应的动力学参数。通过 PM3 计算，优化了立体应变金属卟啉及其氧化中间产物的结构。几何分析表明，在形成额外络合物并与过氧化物反应时，大孔的变形会增加。

  DOI：

  10.1007/s11176-005-0321-z

文献信息

• Effect of pyridine on the reaction of “spanned” zinc porphyrin with organic peroxides
  作者：S. V. Zaitseva、S. A. Zdanovich、O. I. Koifman

  DOI：10.1134/s1070363207070213

  日期：2007.7

  The reaction of "spanned" zinc porphyrin with organic peroxides in the presence of pyridine at 298 K was studied. The kinetic characteristics of the reaction were obtained. The presence of pyridine favors the formation of the zinc chlorin complex. The nature of the nitrogen base affects the character and rate of the reactions of the zinc porphyrin with peroxide. The structures of the sterically strained metal porphyrin and of the chlorin complex formed in the reaction were optimized by PM3 calculations. As follows from the geometric structure of the macrocyclic compounds, the deformations of the macroring enhance in going from zinc porphyrin to zinc chlorin.
• ——
  作者：S. V. Zaitseva、S. A. Zdanovich、T. A. Ageeva、O. A. Golubchikov、A. S. Semeikin

  DOI：10.1023/a:1009538009930

  日期：——

  Spectrophoiometric titration and computer simulation were used to study how the nature of porphyrin and extra ligand affect the formation of extra complexes of zincporphyrins in o-xylene. The compounds under study were zincporphyrins (ZnP) with different substituents and phenyl radicals in meso-positions (zinc-5,15-(p-butyloxyphenyl)-2,8, 12,18-tetramethyl-3,7,13,17-tetraethylporphyrin (ZnPl), zinc-5,15-(p-butyloxyphenyl)-2,8, 12,18-tetramethyl-3,7,13,17-tetrabutylporphyrin (ZnP2) zinctetraphenylporphine (ZnP3), and zinc complexes with overlapped porphyrin (ZnP4). N-Methylimidazole, imidazole, pyridine, 3,5-dimethylpyrazole, and dimethylformamide were used as extra ligands (L). The strength of Zn-L bonding was found to decrease in extra complexes (L)ZnP in the series of ZnP as follows: ZnP4 > ZnP1 > ZnP2 > ZnP3. It was established that the stability constant (logK(st)) for sterically nonstressed complexes (L)ZnP4 linearly increases with growth in the extra ligand basicity (log KBH+) and is proportional to the shift of the main absorption bands (Delta lambda) in the electronic spectra of extra complexes of zinctetraphenylporphine. For spatial ly distorted (L)ZnP1, (L)ZnP2, and (L)ZnP3, the values of logK(st) and log KBH+, as well as logK(St) and Delta lambda, change symbatically. The geometric structure and energy characteristics of pentacoordinated zincporphyrins were calculated by quantum-chemical methods. Correlations were established between the calculated values of the energy of the interaction of the central metal atom with the extra ligand molecule and the stability of the extra complexes of zincporphyrins.
• Influence of electronic and geometric factors on the redox properties of the blocked zinc porphyrinates in the reaction with organic peroxides
  作者：O. R. Simonova、S. A. Zdanowich、S. V. Zaitseva

  DOI：10.1134/s1070363210120182

  日期：2010.12

  By an example of the reaction of intermolecular interaction of organic peroxides with blocked zinc porphyrinates we studied the effect of the macrocycle electronic and conformational features on the redox properties. Kinetics and mechanism of the reaction were studied. Using the calculated geometric characteristics of the isolated molecules of reactants and reaction intermediates, we evaluated a degree of their deformation. An increase in the steric strain in the macrocycle is shown to increase the rate of redox process.