H4TPP(2+) | 18099-04-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四吡咯及其衍生物
• 英文名称: H4TPP(2+)
• 英文别名: cationic form of α,β,γ,δ-meso-tetraphenylporphine；tetraphenylporphyrin dication；tetraphenylporphyrin；α,β,γ,δ-Tetraphenyl-porphin-disaeure
• CAS: 18099-04-2
• 化学式: C₄₄H₃₂N₄
• 分子量: 616.765
• InChiKey: YNHJECZULSZAQK-LWQDQPMZSA-O

计算性质

• 辛醇/水分配系数(LogP)：
  11.44
• 重原子数：
  48.0
• 可旋转键数：
  4.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  57.36
• 氢给体数：
  2.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  H4TPP(2+) 在 盐酸 作用下， 以 十二烷 为溶剂， 生成 tetraphenylporphyrin
  参考文献：
  名称：

  Direct Spectrophotometric Measurement of Demetalation Kinetics of 5,10,15,20-Tetraphenylporphyrinatozinc(II) at the Liquid−Liquid Interface by a Centrifugal Liquid Membrane Method

  摘要：

  通过一种新的原位分光光度法--离心液膜法，研究了十二烷-水酸界面上 5,10,15,20-四苯基卟啉（H2TPP）的质子化和 5,10,15,20-四苯基卟啉-锌（II）（ZnTPP）的脱金属的平衡和动力学，离心液膜法可在旋转玻璃池中提供超薄两相液膜体系。通过光谱变化直接测量了 H2TPP 在主体十二烷相中的消耗量和吸附在液-液界面上的二质子化聚集体 (H4TPP2+)n 的生成量。在 298 K 时，H4TPP2+ 的界面聚集和 ZnTPP 的脱金属的平衡常数分别为 log(Ke1/dm6 mol-2) = 2.14 ± 0.07 和 log(Ke2/dm9 mol-3) = -6.05 ± 0.04。观察到的 ZnTPP 脱金属速率常数取决于酸度函数的一阶，并认为决定速率的步骤是在液-液界面形成单质子化中间体 [ZnTPPH]+。在 H4TPP2+ 的聚集过程中，速率决定步骤是由 H2TPP 在主体十二烷相中的分子扩散控制的。

  DOI：

  10.1021/ac971353s
• 作为产物：
  描述：

  (5,10,15,20-tetraphenylporphyrinato)2Th 以 乙醇 、 溶剂黄146 为溶剂， 生成 H4TPP(2+)
  参考文献：
  名称：

  Andrianova, L. G.; Berezin, B. D.; Lomova, T. N., Doklady Chemistry, 1991, vol. 318, p. 111 - 114

  摘要：

  DOI：

文献信息

• Two-Phase Stopped-Flow Measurement of the Protonation of Tetraphenylporphyrin at the Liquid−Liquid Interface
  作者：Hirohisa Nagatani、Hitoshi Watarai

  DOI：10.1021/ac9506342

  日期：1996.4.1

  at the liquid-liquid interface, and the diprotonated TPP (H(2)TPP(2+)) formed was adsorbed there. In order to determine the rate-determining process, changes in absorbance at the absorption maximum wavelengths of TPP and H(2)TPP(2+) were analyzed. The obtained rate constant for the decrease of TPP in the organic phase, 21 +/- 2 s(-1), was in agreement with that for the increase of diprotonated TPP at

  采用停流法研究了在由十二烷和三氯乙酸水溶液（TCA）组成的分散两相体系中四苯基卟啉（TPP）的质子化形式的形成速率。质子化反应在液-液界面处发生，形成的双质子化TPP（H（2）TPP（2+））被吸附在那里。为了确定速率确定过程，分析了TPP和H（2）TPP（2+）的最大吸收波长处的吸光度变化。获得的有机相中TPP降低的速率常数为21 +/- 2 s（-1），与界面上双质子化TPP的升高速率常数为20 +/- 3 s（-1）一致。观察到的速率常数没有显示出对TPP和酸的浓度的任何依赖性。
• Demetalation of (5,10,15,20-Tetraphenylporphyrinato)iron Complexes: Effect of Substituents at the<i>o</i>-Positions of Phenyl Groups
  作者：Etsuo Hasegawa、Eriko Matsubuchi、Eishun Tsuchida

  DOI：10.1246/bcsj.64.2289

  日期：1991.7

  of a series of (5,10,15,20-tetrahenylporphyrinato)iron(III) complexes having bulky substituents at the o-positions of phenyl rings was studied in acetic acid in the presence of iron(II) chloride and HCl. The reaction occurred simultaneously with the reduction of Fe(III) porphyrin to Fe(II) porphyrin, since no demetalation was observed without iron(II) chloride. The pseudo-first-order rate constants

  在氯化铁 (II) 和 HCl 存在下，在乙酸中研究了一系列 (5,10,15,20-四苯基卟啉基) 铁 (III) 配合物的脱金属反应，这些配合物在苯环的邻位具有大量取代基。该反应与 Fe(III) 卟啉还原为 Fe(II) 卟啉同时发生，因为在没有氯化铁 (II) 的情况下没有观察到脱金属。用分光光度法测定的准一级速率常数随着苯环上 o 取代基的体积增加而降低。产物的阻转异构体结构由高分辨率 NMR 测量确定。
• Lomova, T. N.; Berezin, B. D., Russian Journal of Inorganic Chemistry, 1979, vol. 24, p. 874 - 878
  作者：Lomova, T. N.、Berezin, B. D.

  DOI：——

  日期：——
• Oxovanadium(V)-meso-tetraphenylporphine
  作者：Martin Hoch、Dieter Rehder、Carola Weidemann

  DOI：10.1016/s0020-1693(00)80056-0

  日期：1984.5
• A proton NMR study of the reactions with acid of meso-tetraphenylporphyrins with various numbers of 4-(dimethylamino) groups
  作者：Robert I. Walter、Emmanuel C. A. Ojadi、Henry Linschitz

  DOI：10.1021/j100152a039

  日期：1993.12

  Proton NMR spectroscopy has been used to study the protonation of meso-tetraphenylporphyrins with zero, one, or four para dimethylamino substituents. Changes in the spectra are similar for corresponding protons through this series of compounds. We give the following interpretations. The internal pyrrolenine nitrogen atoms always add two protons before any peripheral dimethylamino groups react. There is no evidence for a monoprotonated intermediate between the free base and diprotonated porphyrin in the chloroform-trifluoroacetic acid solvent system used. The chemical shifts of the NMR signals of the internal N-H protons are strongly acid-dependent and suggest a loss of aromatic ring current at the porphyrin core at intermediate acid concentrations. Changes in chemical shifts of protons on the periphery of these aromatic systems are much smaller and in the opposite sense. The signals of the pyrrole H(beta) protons move discontinuously upfield upon diprotonation and then drift continuously downfield as acid concentration is increased beyond that required for diprotonation. These changes are also in the directions to be expected if aromatic ring currents of the porphyrin decrease to a minimum at the acid concentration at which the internal nitrogen atoms are fully protonated. We suggest that this is due to the known distortion from planarity of the diprotonated tetraarylporphyrin aromatic system. Signals of protons attached to the meso-substituted aromatic rings move unidirectionally downfield as acid concentration increases.