oxo(acetato)molybdenum(V) tetraphenylporphyrin | 77320-98-0

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: oxo(acetato)molybdenum(V) tetraphenylporphyrin
• 英文别名: acetato(5,10,15,20-tetraphenylporphinato)oxomolibdenum(V)
• CAS: 77320-98-0
• 化学式: C₄₆H₃₁MoN₄O₃
• 分子量: 783.717
• InChiKey: VYCRQZDSHONDCX-NBICUONBSA-M

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  oxo(acetato)molybdenum(V) tetraphenylporphyrin 在 sodium nitrite 作用下， 以 二氯甲烷 、 水 为溶剂， 生成 oxo(nitrito)molybdenum(V) tetraphenylporphyrin
  参考文献：
  名称：

  激光闪光光解法研究四苯基钼卟啉的光化学：光诱导的羰基钼和羰基钼（V）四苯基卟啉的钼-氧键均质

  摘要：

  Photolysis of oxoethoxomolybdenum(V) tetraphenylporphyrin (O = Mo(V)(TPP)OC2H5) in a degassed mixture of 9:1 toluene-ethanol gives rise to the homolysis of the Mo-OC2H5 bond with the yield 0.03 to produce oxomolybdenum(IV) tetraphenylporphyrin (O = Mo(IV)TPP) as a stable product. Oxo(nitrito)molybdenum(V) tetraphenylporphyrin (O = Mo(V)(TPP)ONO) in toulene also undergoes photochemical cleavage of the Mo-ONO bond with the yield 0.28 to give O = Mo(IV)TPP and NO2, which recombine to regenerate O = Mo(V)(TPP)ONO. The quantum yield measurements in the temperature range 300-77 K have shown that the activation energies for the photocleavage of the Mo-OC2H5 and Mo-ONO bonds were 5.4 and 8.0 kcal mol-1, respectively. The lowest excited state of O = Mo(V)(TPP)OC2H5, presumably ascribable to the tripquartet state, is detected by the laser photolysis at 77 K. Because of the fact that the quantum yield for the photocleavage of the Mo-OC2H5 bond upon Q-band irradiation is very low in comparison with those obtained upon irradiation of the Soret and CT bands, it is concluded that the lowest excited state is not responsible for the photocleavage. The photoproduct O = Mo(IV)TPP is found to react with oxygen, resulting in formation of the dioxygen adduct. The adduct gradually changes to the mu-oxo dimer [O = Mo(V)TPP]2O. The structure of the dioxygen adduct is discussed on the basis of optical and ESR measurements.

  DOI：

  10.1021/j100180a035
• 作为产物：
  描述：

  methanol,oxomolybdenum,5,10,15,20-tetraphenyl-21,22-dihydroporphyrin 在 CH₃COOH 作用下， 以 二氯甲烷 为溶剂， 以69%的产率得到oxo(acetato)molybdenum(V) tetraphenylporphyrin
  参考文献：
  名称：

  Transition-metal complexes of pyrrole pigments. 18. Redox behaviors of oxomolybdenum(V) complexes formed with macrocyclic tetrapyrroles

  摘要：

  DOI：

  10.1021/ic50221a060

文献信息

• Transition-metal Complexes of Pyrrole Pigments. XIX. Electrochemical and Coordination Behaviors of (5,10,15,20-Tetraphenyl porphinato)niobium(V) Complexes
  作者：Yoshihisa Matsuda、Sunao Yamada、Takashi Goto、Yukito Murakami

  DOI：10.1246/bcsj.54.452

  日期：1981.2

  The redox chemistry of acetato(5,10,15,20-tetraphenylporphinato)oxoniobium(V) (1) was investigated in dichloromethane by means of cyclic voltammetry and controlled potential electrolysis. One-electron reduction potentials were observed at −0.89, −1.05, and −1.41 V vs. SCE for the range from 0 to −2.0 V; the reduction of niobium(V) to niobium(III) occurred prior to ligand-reduction. The potential separation

  通过循环伏安法和控制电位电解，在二氯甲烷中研究了乙酰基（5,10,15,20-四苯基卟吩合）氧铌 (V) (1) 的氧化还原化学。在 -0.89、-1.05 和 -1.41 V 相对于 SCE 的 0 至 -2.0 V 范围内观察到单电子还原电位；铌 (V) 还原为铌 (III) 发生在配体还原之前。1 的第一和第二金属还原 (ΔE1⁄2) 之间的电位间隔为 0.16 V，而相应钼配合物的 MoVI 和 MoV 物种还原之间的 ΔE1⁄2 为 1.24 V。铌和钼配合物之间的电位差，研究了在氧化还原反应过程中发生的配位结构的变化。