nitrido(5,10,15,20-tetraphenylporphyrinato)chromium(V) | 84174-79-8

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: nitrido(5,10,15,20-tetraphenylporphyrinato)chromium(V)
• 英文别名: nitridochromium(V) meso-tetraphenylporphyrinate
• CAS: 84174-79-8
• 化学式: C₄₄H₂₈CrN₅
• 分子量: 678.736
• InChiKey: RLQWDGAFQSSYLD-YKKPBKTHSA-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

• 作为反应物：
  描述：

  nitrido(5,10,15,20-tetraphenylporphyrinato)chromium(V) 在 氧气 作用下， 以 苯 为溶剂， 以0%的产率得到Cr(II)(meso-tetraphenylporphyrinato)
  参考文献：
  名称：

  Pyrolytic reactions of azidochromium(III) porphyrins and azidoiron(III) porphyrins in the solid state

  摘要：

  Azidochromium(III) tetraphenylporphyrin. Cr(III)(tpp)N3 (tpp = 5,10,15,20-tetraphenylporphyrinato), and azidoiron(III) tetraphenylporphyrin, Fe(III)(tpp)N3, in the solid state, were pyrolysed under 10(-5) -10(-6) torr at around 250-degrees-C, liberating nitrogen gas to afford Cr(II)(tpp) and Fe(II)(tpp) as final products, respectively. Cr(v)(tpp)N formed in the process of the Cr(III)(tpp)N3 pyrolysis is reduced to Cr(II)(tpp), although pure Cr(v)(tpp)N prepared independently is not pyrolysed under the same conditions. In the presence of dioxygen in the toluene solutions of these pyrolysed products, Cr(IV)(tpp)O or [Fe(tpp)]2O is formed. The mechanisms of these reactions in the solid state are discussed in comparison with those in solution.

  DOI：

  10.1016/s0277-5387(00)80159-x
• 作为产物：
  描述：

  在 2,4,6-tri-tert-butylphenoxyl 作用下， 以 氟苯 为溶剂， 反应 12.0h， 以12 mg的产率得到nitrido(5,10,15,20-tetraphenylporphyrinato)chromium(V)
  参考文献：
  名称：

  削弱 NH3 配体的 N-H 键：三重氢原子抽象形成氮化铬 (V)

  摘要：

  弱化和断裂 N-H 键对于改进分子氨 (NH 3 ) 氧化催化剂至关重要。我们报告了双（氨）铬卟啉配合物 Cr(TPP)(NH 3 ) 2和 Cr(TMP)(NH 3 ) 2 (TPP = 5,10,15,20-四苯基)的合成和 H 原子提取反应- meso -porphyrin 和 TMP = 5,10,15,20- tetramesityl- meso - porphyrin) 使用庞大的芳氧基自由基。三重 H 原子提取反应导致 Cr V (por)(≡N) 的形成，氮化物衍生自 NH 3，如 UV-vis 和 IR 以及 Cr(TPP)(≡N) 的单晶结构测定所示。该铬 (V) 氮化物络合物的后续氧化导致形成 Cr III (por)，并断开 Cr≡N 键。计算分析说明了从 Cr II到 Cr V的进展，并评估了从 Cr II -NH 3中提取 H 原子以生成 Cr V ≡N 的能量学。Cr

  DOI：

  10.1021/acs.inorgchem.2c01115

文献信息

• Pyrolysis of Azidomanganese(III) Porphyrin Affording Nitridomanganese(V) Porphyrin
  作者：Yuichi Yamamoto、Taira Imamura、Toru Suzuki、Masatoshi Fujimoto

  DOI：10.1246/cl.1988.261

  日期：1988.2.5

  Azidomanganese(III) meso-tetraphenylporphyrin, MnIII (tpp)N3, in the solid state was pyrolyzed around 236 °C to yield nitridomanganese (V) meso-tetraphenylporphyrin, MnV (tpp)N.

  固态叠氮锰（III）介四苯基卟啉 MnIII (tpp)N3 在 236 ℃ 左右热解，生成硝基锰（V）介四苯基卟啉 MnV (tpp)N。
• Magnetic Relaxations of Chromium Nitride Porphyrinato Complexes Driven by the Anisotropic g‐Factor
  作者：Tsutomu Yamabayashi、Yoji Horii、Zhao‐Yang Li、Masahiro Yamashita

  DOI：10.1002/chem.202303082

  日期：2024.1.11

  Detailed analyses for vibrational and dynamical magnetism of chromium nitride (CrN2−)-porphyrinato complex revealed that g-value anisotropy accelerates magnetic relaxations greater than the internal magnetic field from nuclear spin does.

  对氮化铬 (CrN 2− )-卟啉配合物的振动和动态磁性的详细分析表明， g值各向异性比核自旋的内部磁场加速磁弛豫的速度更大。
• Neely, Frank L.; Bottomley, Lawrence A., Inorganic Chemistry, 1997, vol. 36, # 24, p. 5432 - 5434
  作者：Neely, Frank L.、Bottomley, Lawrence A.

  DOI：——

  日期：——
• Jin, Takashi; Suzuki, Toru; Imamura, Taira, Inorganic Chemistry, 1987, vol. 26, # 8, p. 1280 - 1285
  作者：Jin, Takashi、Suzuki, Toru、Imamura, Taira、Fujimoto, Masatoshi

  DOI：——

  日期：——
• Stereoelectronic Aspects of Inter-Metal Nitrogen Atom Transfer Reactions between Nitridomanganese(V) and Chromium(III) Porphyrins
  作者：Lawrence A. Bottomley、Frank L. Neely

  DOI：10.1021/ic960919c

  日期：1997.11.1

  Reactions of nitridomanganese(V) porphyrins with chromium(III) porphyrins resulted in the irreversible formation of nitridochromium(V) porphyrins and manganese(III) porphyrins. The progress of these reactions has been followed spectrophotometrically, electrochemically, and spectroscopically by EPR. Kinetic analysis of the spectrophotometric data obtained during these reactions for a variety of substituted porphyrins showed the reactions to be first order in each of the reactants. Rate constants were dependent upon the electronic and steric effects of the porphyrin substituent, upon the identity of the anion bound to the chromium(III) reactant, and upon the solvent dielectric constant. We propose that the mechanism of these nitrogen atom transfer reactions involves the nucleophilic attack of the nitridomanganese porphyrin donor on the cationic chromium(III) porphyrin acceptor facilitating a net, two-electron redox process mediated by a heterobimetallic mu-nitrido intermediate. This report represents the first systematic study of the stereoelectronic effects involved in the complete, inter-metal nitrogen atom transfer between two metalloporphyrins.