oxo(nitrito)molybdenum(V) tetraphenylporphyrin | 136882-00-3

• 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(nitrito)molybdenum(V) tetraphenylporphyrin
• CAS: 136882-00-3
• 化学式: C₄₄H₂₈MoN₅O₃
• 分子量: 770.678
• InChiKey: DVZDAPSLAVGRPQ-NBICUONBSA-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：
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反应信息

• 作为反应物：
  描述：

  oxo(nitrito)molybdenum(V) tetraphenylporphyrin 以 苯 为溶剂， 以25-33的产率得到(5,10,15,20-meso-tetraphenylporphyrinato)oxomolybdenum(IV)
  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：

  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