cloro(2,8,12,18-tetrabutyl-3,7,13,17-tetramethyl-5,15-diazaporphinato)indium(III) | 241131-40-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: cloro(2,8,12,18-tetrabutyl-3,7,13,17-tetramethyl-5,15-diazaporphinato)indium(III)
• 英文别名: 2,8,12,18-tetrabutyl-3,7,13,17-tetramethyl-5,10-diazaporphinatoindium(III) chloride；[(Cl)InMBDAP]；[(2,8,12,18-tetrabutyl-3,17,13,17-tetramethyl-5,15-diazaporphyrinato)InCl]；5,9,15,19-Tetrabutyl-22-chloro-4,10,14,20-tetramethyl-2,12,21,23,24,25-hexaza-22-indahexacyclo[9.9.3.13,6.113,16.08,23.018,21]pentacosa-1(20),2,4,6(25),7,9,11,13(24),14,16,18-undecaene
• CAS: 241131-40-8
• 化学式: C₃₈H₅₀ClInN₆
• 分子量: 741.128
• InChiKey: OAOLSBHGTCWZDH-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  8.89
• 重原子数：
  46
• 可旋转键数：
  12
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  57.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  cloro(2,8,12,18-tetrabutyl-3,7,13,17-tetramethyl-5,15-diazaporphinato)indium(III) 在 sulfuric acid 作用下， 以 硫酸 为溶剂， 生成 indium
  参考文献：
  名称：

  摘要：

  Stability of chloro(octaphenyltetraazaporphinato)indium(III) and chloro(2,8,12,18-tetrabutyl-3,7,13,17-tetramethyl-5,15-diazaporphinato)indium(III) in 90-98 % aqueous sulfuric acid was studied. Kinetic parameters of solvoprotolytic dissociation of the complexes were determined, and a mechanism of the reaction was proposed. Diaza substitution results in more stable complexes than tetraaza substitution. The state of chloro(2,8,12,18-tetrabutyl-3,7,13,17-tetramethyl-5,15-diazaporphinato)indium(III) in a proton-donor medium was studied to show that the acid-base interaction involves one by one two meso-nitrogen atoms. Dissociation constants of the resulting acid forms were determined.

  DOI：

  10.1023/a:1013931826723

文献信息

• Study of acid-base interactions of mono- and diazaporphyrin indium complexes with acetic and trifluoroacetic acids by 1H NMR and electronic spectroscopy
  作者：P. A. Stuzhin、S. S. Ivanova、I. S. Migalova

  DOI：10.1007/s11176-005-0028-1

  日期：2004.9

  Indium complex of 13,17-dibutyl-2,3,7,8,12,18-hexamethyl-5-azaporphyrin (Cl)InMAP was synthesized, and acid-base interactions of the meso-nitrogen atoms in (Cl)InMAP and its diaza analog (Cl)InDAP with acetic and trifluoroacetic acids were studied by 1H NMR and electronic spectroscopy. Depending on the medium, the complexes and proton-donor species HA give rise to acid solvates >N⋅⋅⋅(HA)n which are converted to final acid-base interaction products, H-complexes >N⋅⋅⋅H+⋅⋅⋅A−(HA)m or ionic associates >NH+⋅⋅⋅A−(HA)l , as the acidity of the medium rises. In acetic acid solution, the acid solvates derived from more basic (Cl)InMAP exist in equilibrium with the H-associates (pK a1 = 4.45±0.03). From (Cl)InDAP, the corresponding H-associates are formed only in the presence of H2SO4 (pK a1 = 2.10±0.03). In more polar media (solutions of trifluoroacetic acid in methylene chloride), ionic associates are formed, which involve one [(Cl)InMAP, pK 1 = 2.46±0.02] or two meso-nitrogen atoms [(Cl)InDAP, pK 1 = 2.11±0.03, pK 2 = 0.41±0.04).

  合成了 13,17-二丁基-2,3,7,8,12,18-六甲基-5-氮杂卟啉的铟络合物 (Cl)InMAP，并通过 1H NMR 和电子能谱研究了 (Cl)InMAP 及其重氮类似物 (Cl)InDAP 中的中氮原子与乙酸和三氟乙酸的酸碱相互作用。随着介质酸度的升高，络合物和质子供体物种 HA 会产生酸溶胶>N⋅⋅⋅(HA)n，并转化为最终的酸碱相互作用产物、H-络合物>N⋅⋅⋅H+⋅⋅⋅A-(HA)m 或离子络合物>NH+⋅⋅⋅A-(HA)l。在醋酸溶液中，由碱性较强的(Cl)InMAP 生成的酸溶质与 H-同系物（pK a1 = 4.45±0.03）处于平衡状态。(Cl)InDAP 只有在有 H2SO4 存在时才会形成相应的 H-同系物（pK a1 = 2.10±0.03）。在极性更强的介质（三氟乙酸在二氯甲烷中的溶液）中，会形成涉及一个[(Cl)InMAP, pK 1 = 2.46±0.02] 或两个介氮原子[(Cl)InDAP, pK 1 = 2.11±0.03, pK 2 = 0.41±0.04]的离子联营体。