2,3,12,13-tetrakis(trifluoromethyl)-5,10,15,20-tetraphenylporphyrinatozinc(II) | 479679-95-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,3,12,13-tetrakis(trifluoromethyl)-5,10,15,20-tetraphenylporphyrinatozinc(II)
• CAS: 479679-95-3
• 化学式: C₄₈H₂₄F₁₂N₄Zn
• 分子量: 950.116
• InChiKey: APVJLGAQCAGAEE-WUTQRECDSA-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：

  乙醇 、 2,3,12,13-tetrakis(trifluoromethyl)-5,10,15,20-tetraphenylporphyrinatozinc(II) 以 乙醇 、 氯仿 为溶剂， 生成 [Zn(II)(2,3,12,13-tetrakis(trifluoromethyl)-5,10,15,20-tetraphenylporphyrinato)(EtOH)]*2EtOH
  参考文献：
  名称：

  Synthesis, Crystal Structures, and Redox Potentials of 2,3,12,13-Tetrasubstituted 5,10,15,20-Tetraphenylporphyrin Zinc(II) Complexes

  摘要：

  Zinc(II) complexes of antipodal beta-tetrasubstituted meso-tetraphenylporphyrin with trifluoromethyl (Zn(TPP(CF3)(4)) (1a)), bromine (Zn(TPPBr4) (2a)), and methyl groups (Zn(TPP(CH3)(4)) (3a)) were synthesized in order to examine the steric and the electronic effects of trifluoromethyl groups on the macrocycle. The analysis of X-ray crystal structures of the five-coordinate complexes Zn(TPP(CF3)(4))(EtOH)(3) (1b), Zn(TPPBr4)(MeOH)(DMF) (2b), and Zn(TPP(CH3)(4))(THF)(1.6)(CHCl3)(0.4) (3b) revealed distorted macrocyclic cores where significant differences in the Zn-N distance between the beta-substituted and the non-beta-substituted side were observed, The difference was significant in 1b due to the strong steric interactions among the peripheral substituents and the electronic effects of trifluoromethyl groups. The macrocycles of 1b-3b are saddle-distorted and slightly ruffled due to the five-coordination of zinc(II) and the peripheral substitution. Distortion of the macrocycles of 2b and 3b were modest. On the other hand, distortion in 1b was severe due to the peripheral strain. Cyclic voltammetric measurements of the four-coordinate complexes Zn(TPP) and 1a-3a were performed and their redox potentials were analyzed together with previously reported potentials of Zn(TPP(CN)(4)). The oxidation potential of la did not gain as much as expected from the electron-withdrawing effect of the four trifluoromethyl groups, The HOMO-LUMO gap of 1a was very small (1.5 V) and cannot just be explained by macrocyclic distortion. The magnitude of this gap is very similar to that of Zn(TPP(CN)(4)). Compound 2a also exhibited a modest gap contraction. Compound 3a was easier to oxidize and harder to reduce than Zn(TPP), even though the HOMO-LUMO gap of 3a was similar to that of Zn(TPP).

  DOI：

  10.1021/ic020339h
• 作为产物：
  描述：

  zinc(II) acetate dihydrate 、 5,10,15,20-tetraphenyl-2,3,12,13-tetrakis(trifluoromethyl)porphyrin 以 甲醇 、 氯仿 为溶剂， 以98%的产率得到2,3,12,13-tetrakis(trifluoromethyl)-5,10,15,20-tetraphenylporphyrinatozinc(II)
  参考文献：
  名称：

  Synthesis, Crystal Structures, and Redox Potentials of 2,3,12,13-Tetrasubstituted 5,10,15,20-Tetraphenylporphyrin Zinc(II) Complexes

  摘要：

  Zinc(II) complexes of antipodal beta-tetrasubstituted meso-tetraphenylporphyrin with trifluoromethyl (Zn(TPP(CF3)(4)) (1a)), bromine (Zn(TPPBr4) (2a)), and methyl groups (Zn(TPP(CH3)(4)) (3a)) were synthesized in order to examine the steric and the electronic effects of trifluoromethyl groups on the macrocycle. The analysis of X-ray crystal structures of the five-coordinate complexes Zn(TPP(CF3)(4))(EtOH)(3) (1b), Zn(TPPBr4)(MeOH)(DMF) (2b), and Zn(TPP(CH3)(4))(THF)(1.6)(CHCl3)(0.4) (3b) revealed distorted macrocyclic cores where significant differences in the Zn-N distance between the beta-substituted and the non-beta-substituted side were observed, The difference was significant in 1b due to the strong steric interactions among the peripheral substituents and the electronic effects of trifluoromethyl groups. The macrocycles of 1b-3b are saddle-distorted and slightly ruffled due to the five-coordination of zinc(II) and the peripheral substitution. Distortion of the macrocycles of 2b and 3b were modest. On the other hand, distortion in 1b was severe due to the peripheral strain. Cyclic voltammetric measurements of the four-coordinate complexes Zn(TPP) and 1a-3a were performed and their redox potentials were analyzed together with previously reported potentials of Zn(TPP(CN)(4)). The oxidation potential of la did not gain as much as expected from the electron-withdrawing effect of the four trifluoromethyl groups, The HOMO-LUMO gap of 1a was very small (1.5 V) and cannot just be explained by macrocyclic distortion. The magnitude of this gap is very similar to that of Zn(TPP(CN)(4)). Compound 2a also exhibited a modest gap contraction. Compound 3a was easier to oxidize and harder to reduce than Zn(TPP), even though the HOMO-LUMO gap of 3a was similar to that of Zn(TPP).

  DOI：

  10.1021/ic020339h