NbO(5,10,15,20-tetraphenylporphyrinato)(OAc) * AcOH | 72394-78-6

• 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: NbO(5,10,15,20-tetraphenylporphyrinato)(OAc) * AcOH
• 英文别名: acetato-oxo-(5,10,15,20-tetraphenylporphyrinato)niobium(V)-acetic acid (1/1)
• CAS: 72394-78-6；64398-99-8
• 化学式: C₂H₄O₂*C₄₆H₃₁N₄NbO₃
• 分子量: 840.736
• InChiKey: PPJKLKKBFZIVRE-GVHKZQBISA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  NbO(5,10,15,20-tetraphenylporphyrinato)(OAc) * AcOH 、 邻苯二酚 以 正己烷 、 二氯甲烷 为溶剂， 以98%的产率得到Nb(5,10,15,20-tetraphenylporphyrinato)(catecholate(2-))(catecholate(1-)) * 0.50 hexane * CH2Cl2
  参考文献：
  名称：

  Cleavage of the Nb:O Bond of Oxoniobium(V) Porphyrins. Synthesis and Characterization of Novel Niobium(V) Porphyrins with Two Distinct Catechols

  摘要：

  A novel catecholato complex, Nb-V(tpp)(cat)(Hcat), where cat and Heat are two distinct catechol ligands (a bidentate catecholate dianion and a monodentate catecholate monoanion, respectively) and tpp is 5,10,15,20-tetraphenylporphyrin dianion, has been isolated in the reaction of NBV(tpp)(O)(AcO) with catechol, where AcO is an acetato ligand. Its molecular structure has been determined by X-ray crystallography. Crystal data: monoclinic, space group P2(1)/c, Z = 4, a = 14.592(3) Angstrom, b = 23.46(1) Angstrom, c = 14.415(4) Angstrom, beta = 100.95(2)degrees, R = 0.079. The molecular structure was confirmed to have no oxo ligand, and in this respect it is unique among the niobium(V) porphyrins. The bidentate and monodentate ligands are located on the same side of the porphyrin ring. The heptacoordinate niobium atom is bonded to the four gyrrole nitrogen atoms and to three oxygen atoms in the catechols. The niobium atom is displaced by 1.02 Angstrom from the mean plane of the four nitrogen atoms. The structure of the complex in solution and the mechanism of the Nb = O cleavage were investigated by means of H-1-NMR spectroscopy. The bidentate catechol is oriented in C-s symmetry with respect to the porphyrin plane, and the monodentate catechol is located perpendicularly to both the bidentate catechol and the porphyrin plane. Two intermediates with the bidentate catechol were observed after addition of 2 equiv of catechol to Nb(tmp)(O)(AcO) at -30 degrees C, where tmp denotes the 5, 10, 15, 20-tetramesitylporphyrin dianion. These intermediates were determined to be Nb(tmp)(cat)(OH) and Nb(tmp)(cat)(AcO). Thus, the Nb = O bond of Nb(tmp)(O)(AcO) was easily cleaved to create the two intermediates. We propose a unique route to the Nb = O cleavage that involves an intramolecular electron transfer from the catechol ligand coordinated at the first stage through a ligand exchange with AcO. Both protonation and electron transfer to the Nb = O moiety play important roles in the Nb = O cleavage.

  DOI：

  10.1021/ic00123a025
• 作为产物：
  描述：

  tri-μ-oxo-bis(5,10,15,20-tetraphenylporphyrinatoniobium(V)) 以 溶剂黄146 为溶剂， 以92%的产率得到NbO(5,10,15,20-tetraphenylporphyrinato)(OAc) * AcOH
  参考文献：
  名称：

  卟啉铌（V）的合成。三-μ-氧代-双[5,10,15,20-四苯基卟啉铌（V）]和乙酸-（5,10,15,20-四苯基卟啉铌）铌（V）-乙酸的晶体结构（1 / 1）

  摘要：

  NbCl 5对卟啉（H 2 L）的作用随后发生水解，导致形成复合物[（NbL）2 O 3 ]。当用乙酸处理时，该络合物又产生通式[NbL（O）（O 2 CMe）]· x MeCO 2 H的金属卟啉。[{Nb（tpp）} 2 O 3 ]·4C 2的晶体结构X射线分析了H 4 Cl 2（1b）和[Nb（tpp）O（O 2 CMe）]·MeCO 2 H（2b）（tpp是5,10,15,20-四苯基卟啉的二价阴离子）衍射法。（2b）的晶体是三斜晶系，空间群P，a = 16.645（6），b = 11.332（4），c = 11.868（4）Å，α= 105.93（6），β= 100.54（4），γ= 105.05（4）°，Z = 2.（1b）的晶体是正交晶体，空间群Pccn，其a = 31.802（9），b = 11.595（5），c = 23.431（7）Å和Z =4。这两种结构都是由衍射仪数据

  DOI：

  10.1039/dt9790001306