2,3,12,13-tetramethyl-5,10,15,20-tetraphenylporphyrinatozinc(II) | 479679-99-7

• 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: 2,3,12,13-tetramethyl-5,10,15,20-tetraphenylporphyrinatozinc(II)
• 英文别名: Zn(2,3,12,13-tetramethyl-5,10,15,20-tetraphenylporphyrin(2-))
• CAS: 479679-99-7
• 化学式: C₄₈H₃₆N₄Zn
• 分子量: 734.231
• InChiKey: ZRJAFTCQQZILOE-FPEGMCNOSA-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

• 作为产物：
  描述：

  2,3,12,13-tetrabromo-5,10,15,20-tetrakis(phenyl)porphyrin 在 四(三苯基膦)钯 、 potassium carbonate 作用下， 以 四氢呋喃 、 甲醇 、 氯仿 、 甲苯 为溶剂， 反应 72.5h， 生成 2,3,12,13-tetramethyl-5,10,15,20-tetraphenylporphyrinatozinc(II)
  参考文献：
  名称：

  氟功能化ZnTPPs的合成与研究

  摘要：

  五氟化锌四苯基卟啉衍生物，氟化物的所有邻位中观苯环（Zn(II)-5,10,15,20-四（2,6-二氟苯基）卟啉）或β-具有两个、四个、六个或八个氟基团的位置（2,3-二氟-5,10,15,20-四苯基卟啉, 7, 8,17,18-四氟-5,10,15,20-四苯基卟啉, 7 ,8,12,13,17,18-hexafluoro-5,10,15,20-四苯基卟啉和 2,3,7,8,12,13,17,18-octafluoro-5,10,15,20 -四苯基卟啉，分别）进行了研究，以探测氟在表面合成方法中的作用。此外，更大的取代基已用于 7,8,17,18-四溴-5,10,15,20-四苯基卟啉和 7,8,17,18-四甲基-5,10,15,20-四苯基卟啉，用于与相应的含氟化合物直接比较。报告了化合物的合成和电子结构表征，使用紫外-可见吸收和荧光光谱以及基态分子特性的电子结构计算。探索了氟

  DOI：

  10.1142/s1088424622500146

文献信息

• Synthesis, Crystal Structures, and Redox Potentials of 2,3,12,13-Tetrasubstituted 5,10,15,20-Tetraphenylporphyrin Zinc(II) Complexes
  作者：Yuichi Terazono、Brian O. Patrick、David H. Dolphin

  DOI：10.1021/ic020339h

  日期：2002.12.1

  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).