(5,10,15,20-meso-tetraphenylporphyrinato)oxomolybdenum(IV) | 33519-60-7

• 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: (5,10,15,20-meso-tetraphenylporphyrinato)oxomolybdenum(IV)
• 英文别名: oxo-molybdenum(IV) 5,10,15,20-tetraphenylporphyrin；tetraphenylporphyrinato Mo；oxo(TPP)Mo(IV)
• CAS: 33519-60-7
• 化学式: C₄₄H₂₈MoN₄O
• 分子量: 724.673
• InChiKey: ZFMMNDRKVYLRMQ-YKKPBKTHSA-N

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：
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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：

  (5,10,15,20-meso-tetraphenylporphyrinato)oxomolybdenum(IV) 在 氧气 作用下， 以 甲苯 为溶剂， 生成 Mo(O)(5,10,15,20-tetraphenylporphyrinato)O2
  参考文献：
  名称：

  钼卟啉的新型双氧复合物。氧钼 (IV) 卟啉与分子氧的反应

  摘要：

  通过将分子氧引入氧代钼 (IV) 卟啉、MoIVO(tpp) 和 MoIVO(oep) 的甲苯溶液中，在 -70 °C 左右形成新的分子氧钼卟啉。通过将温度升高到 25 °C，或通过 Soret 波段波长的溶液光照射，可以再生母体氧代钼 (IV) 卟啉。提出了双氧配合物的结构。

  DOI：

  10.1246/cl.1990.2085
• 作为产物：
  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

文献信息

• PHOTOREDLJCTION OF MANGANESE(III), IRON(III), COBALT(III), AND MOLYBDENUM(V) TETRAPHENYLPORPHYRINS IN 2-METHYLTETRAHYDROFURAN
  作者：Taira Imamura、Takashi Jin、Toru Suzuki、Masatoshi Fujimoto

  DOI：10.1246/cl.1985.847

  日期：1985.6.5

  The central metals in the metallotetraphenylporphyrins with axial halo or pseudohalo ligands, MnIII(tpp)X (tpp = 5,10,15,20-tetraphenylporphinato; X = I, Br, Cl, OAc, NCS), FeIII(tpp)Cl, CoIII(tpp)Cl, and MoVO(tpp)X (X = Br, Cl, F, NCS, N3), in 2-methyltetrahydrofuran are photoreduced with visible light at room temperature to form MnII(tpp), FeII(tpp), CoII(tpp), and MoIVO(tpp), respectively.

  轴向含卤或拟卤配体的金属卟啉络合物[MnIII(tpp)X (tpp = 5,10,15,20-四苯基卟吩; X = I, Br, Cl, OAc, NCS)，FeIII(tpp)Cl，CoIII(tpp)Cl，以及MoVO(tpp)X (X = Br, Cl, F, NCS, N3)]在2-甲基四氢呋喃中，室温下可见光照射将其分别还原为MnII(tpp)，FeII(tpp)，CoII(tpp)，和MoIVO(tpp)。
• Reversibility in the Formation of Oxo(peroxo)porphyrinatomolybdenums
  作者：Tetsuaki Fujihara、Koji Hoshiba、Yoichi Sasaki、Taira Imamura

  DOI：10.1246/bcsj.73.383

  日期：2000.2

  in the formation reaction of a series of the oxo(peroxo)porphyrinatomolybdenums, [MoVIO(tmp)(O2)] 1, [MoVIO(tdcpp)(O2)] 2, [MoVIO(ttp)(O2)] 3, [MoVIO(tdmpp)(O2)] 4, and [MoVIO(tpp)(O2)] 5, was studied. In these dioxygen complexes with various porphyrin rings, two complexes, 2 and 4, were newly prepared by the solid-state reactions of corresponding Mo(IV) complexes with O2. All the complexes were characterized

  [MoVIO(tmp)(O2)] 1, [MoVIO(tdcpp)(O2)] 2, [MoVIO(ttp)(O2)] 3, [MoVIO(tmp)(O2)] 1, [MoVIO(tmp)(O2)] 3, [研究了 MoVIO(tdmpp)(O2)] 4 和 [MoVIO(tpp)(O2)] 5。在这些具有各种卟啉环的双氧配合物中，通过相应的 Mo(IV) 配合物与 O2 的固态反应，新制备了两种配合物 2 和 4。所有配合物均通过 IR、1H NMR 和 UV-vis 光谱测量表征。在 O2 与 [MoIVO(tdcpp)] 2r 的反应中，[MoIVO(tdcpp)] 2r 具有大量具有吸电子特性的取代基，在 20°的甲苯中，缔合速率常数确定为 1.2 × 10-2 dm3 mol-1 s-1 C。速率常数的值约为 [MoIVO(tmp)] 1r 的三十分之一，后者也具有庞大的取代基。
• Facile Preparation of Manganese(II) Tetraphenylporphyrin by the Pyrolysis of Dimethoxoraanganese(IV) Tetraphenylporphyrin
  作者：Toru Suzuki、Taira Imamura、Masatoshi Fujimoto

  DOI：10.1246/cl.1988.257

  日期：1988.2.5

  Manganese(II) tetraphenylporphyrin, MnII (tpp) (tpp = meso-tetraphenylporphinato), was afforded by the pyrolysis of MnIV(tpp)(OCH3)2 at ≈180 °C under 10−4–10−5 Torr (1 Torr ≅ 133.3 Pa). The pyrolysis of MoVO(tpp)OR (R = CH3, C2H5) in the solid state yielded MoIVO(tpp).

  在 10-4-10-5 托（1 托≅133.3 帕）条件下，MnIV(tpp)(O )2 在 ≈180 ℃ 热解得到四苯基卟啉锰(II)MnII (tpp)（tpp = 间四苯基卟啉）。在固态下热解 MoVO(tpp)OR（R = CH3，C2H5）得到 MoIVO(tpp)。
• Solid-State Synthesis of Molybdenum and Tungsten Porphyrins and Aerial Oxidation of Coordinated Benzenethiolate to Benzenesulfonate
  作者：Goutam Nandi、Sabyasachi Sarkar

  DOI：10.1021/ic3008377

  日期：2012.6.4

  A new route is developed for the synthesis of molybdenum and tungsten porphyrins using [M(NO)2py2Cl2] (M = Mo, W) as the metal source and TPP (dianion of 5,10,15,20-meso-tetraphenylporphyrin) in the benzoic acid melt. Complexes [MoVO(TPP)(OOCPh)] (1) and [WVO(TPP)(OOCPh)] (2) are isolated in almost quantitative yield. These are characterized by single-crystal X-ray structure analysis, electron paramagnetic

  [M（NO）2 py 2 Cl 2 ]（M = Mo，W）作为金属源和TPP（5,10,15,20-中消旋阴离子）用于合成钼和钨卟啉的新路线-四苯基卟啉）。分离出[Mo V O（TPP）（OOCPh）]（1）和[W V O（TPP）（OOCPh）]（2）几乎是定量的。它们的特征在于单晶X射线结构分析，电子顺磁共振，电子和红外光谱以及磁矩测量。苯硫酚替代了PhCOO -在1，形成一个中间硫醇基络合物，该分子对跨Mo V –SPh键的分子内氧化还原反应作出响应，从而产生[Mo IV O（TPP）]（3）。在过量的苯硫醇下，PhS –与3中的空位配位，在空氧化下，PhS –被氧化为苯磺酸盐，形成[Mo V O（TPP）（O 3 SPh）]（4）。2经历了类似的空中氧化化学反应，尽管速度很慢。
• INTERMEDIATE IN THE REACTION OF OXOMOLYBDENUM(V) TETRAPHENYLPORPHYRIN COMPLEX WITH SUPEROXIDE ION IN APROTIC SOLVENTS
  作者：Taira Imamura、Koichi Hasegawa、Masatoshi Fujimoto

  DOI：10.1246/cl.1983.705

  日期：1983.5.5

  (tpp = meso-tetraphenylporphinato) is reduced by superoxide ion, O2−, to MoIVO(tpp) in 1%(v/v) DMSO–CH2Cl2 medium at 25 °C via an intermediate. The intermediate is suggested to be a dioxygen complex and stably exists in the solution at −72 °C. The oxidation state of the central molybdenum in the intermediate complex reversibly changes with temperature between 4+ at −80 °C and 5+ at 0 °C.

  MoVO(tpp)Br (tpp = meso-tetraphenylporphinato) 在 1%(v/v) DMSO–CH2Cl2 介质中，通过中间体在 25 °C 下被超氧离子 O2− 还原为 MoIVO(tpp)。中间体被认为是双氧配合物，在-72°C 时稳定存在于溶液中。中间配合物中中心钼的氧化态随温度在 -80°C 时的 4+ 和 0°C 时的 5+ 之间可逆地变化。