Mn(meso-tetraphenylporphyrinatodianion)(η1-ONO) | 132438-45-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯啉
• 英文名称: Mn(meso-tetraphenylporphyrinatodianion)(η1-ONO)
• 英文别名: nitritomanganese(III) tetraphenylporphyrin；Mn(meso-tetraphenylporphyrinatodianion)(η¹-ONO)；Mn(TPP)(η¹-ONO)；Mn(tetraphenylporphyrinato)(ONO)；Mn(TPP)(NO2)
• CAS: 132438-45-0
• 化学式: C₄₄H₂₈MnN₅O₂
• 分子量: 713.677
• InChiKey: HRWMBVCUCUADFX-YKKPBKTHSA-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：
  None
• 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：

  Mn(meso-tetraphenylporphyrinatodianion)(η1-ONO) 以 甲苯 为溶剂， 生成 2,3,5,7-四苯基-21H,23H-卟吩锰(2+)盐(1:1)
  参考文献：
  名称：

  Hoshino, Mikio; Nagashima, Yutaka; Seki, Hiroshi, Inorganic Chemistry, 1998, vol. 37, # 10, p. 2464 - 2469

  摘要：

  DOI：
• 作为产物：
  描述：

  2,3,5,7-四苯基-21H,23H-卟吩锰(2+)盐(1:1) 、 二氧化氮 生成 Mn(meso-tetraphenylporphyrinatodianion)(η1-ONO)
  参考文献：
  名称：

  Six-Coordinate Nitrito and Nitrato Complexes of Manganese Porphyrin

  摘要：

  Reaction of small increments of NO2 gas with sublimed amorphous layers of Mn-II(TPP) (TPP = meso-tetra-phenylporphyrinato dianion) in a vacuum cryostat leads to formation of the 5-coordinate monodentate nitrato complex Mn-III(TPP)(eta(1)-ONO2) (II). This transformation proceeds through the two distinct steps with initial formation of the five coordinate O-nitrito complex Mn-III(TPP)(eta(1)-ONO) (I) as demonstrated by the electronic absorption spectra and by FTIR spectra using differently labeled nitrogen dioxide. A plausible mechanism for the second stage of reaction is offered based on the spectral changes observed upon subsequent interaction of (NO2)-N-15 and NO2 with the layered Mn(TPP). Low-temperature interaction of I and II with the vapors of various ligands L (L = O-, S-, and N-donors) leads to formation of the 6-coordinate O-nitrito Mn-III(TPP)(L)(eta(1)-ONO) and monodentate nitrato Mn-III(TPP)(L)(eta(1)-ONO2) complexes, respectively. Formation of the 6-coordinate O-nitrito complex is accompanied by the shifts of the nu(N=O) band to lower frequency and of the nu(N=O) band to higher frequency. The frequency difference between these bands triangle nu = nu(N=-O) - nu(N=O) is a function of L and is smaller for the stronger bases. Reaction of excess NH3 with I leads to formation of Mn(TPP)(NH3)(eta(1)-ONO) and of the cation [Mn(TPP)(NH3)(2)](+) plus ionic nitrite. The nitrito complexes are relatively unstable, but several of the nitrato species can be observed in the solid state at room temperature. For example, the tetrahydrofuran complex Mn(TPP)(THF)(eta(1)-ONO2) is stable in the presence of THF vapors (similar to 5 mm), but it loses this ligand upon high vacuum pumping at RT. When L = dimethylsulfide (DMS), the nitrato complex is stable only to similar to 30 degrees C. Reactions of II with the N-donor ligands NH3, pyridine, or 1-methylimidazole are more complex. With these ligands, the nitrato complexes Mn-III(TPP)(L)(eta(1)-ONO2) and the cationic complexes [Mn(TPP)(L)(2)](+) coexist in the layer at room temperature, the latter formed as a result of NO3- displacement when L is in excess.

  DOI：

  10.1021/ic5014329

文献信息

• Metalloporphyrin photochemistry with matrix isolation
  作者：Kenneth S. Suslick、Jocelyn F. Bautista、Randall A. Watson

  DOI：10.1021/ja00016a029

  日期：1991.7

  ligand appears to be a general mechanism for all metalloporphyrin complexes examined. The formation of metal-oxo species from photolysis of metalloporphyrin oxoanion complexes in solution derives from secondary, thermal reactions. The role of metalloporphyrins in two very separate biological processes, oxoanion reduction (nitrite and sulfite reductases)l-" and hydrocarbon oxidation (cytochrome P450)

  许多金属卟啉氧阴离子配合物的光化学已通过基质分离技术进行了检查，使用冷冻溶剂玻璃和聚合物薄膜。在广泛寻找非配位、非反应性、玻璃化溶剂后，发现 2,2-二甲基丁烷和叔丁基苯的 3:1 混合物在低于 70 K 的温度下工作良好。 或者，在聚合物薄膜中监测金属卟啉的光化学通过在蓝宝石窗口上蒸发甲苯中的金属卟啉溶液，其中含有 pol::甲基丙烯酸甲酯）或聚（a-甲基苯乙烯）。聚合物薄膜具有更大的温度范围的额外优势，即使在室温下也能提供扩散隔离。通过均裂 a 键裂解和轴向配体丢失对金属的光还原似乎是所有金属卟啉配合物的一般机制。金属卟啉氧阴离子配合物在溶液中光解形成的金属氧物种源自二次热反应。金属卟啉在两个非常独立的生物过程中的作用，含氧阴离子还原（亚硝酸盐和亚硫酸盐还原酶）l-" 和碳氢化合物氧化（细胞色素 P450），使我们研究了许多阴离子（包括硝酸盐和亚硝酸盐）的金属卟啉复合物 6 的光化学，
• In Situ FT-IR and UV−vis Spectroscopy of the Low-Temperature NO Disproportionation Mediated by Solid State Manganese(II) Porphyrinates
  作者：Garik G. Martirosyan、Arsen S. Azizyan、Tigran S. Kurtikyan、Peter C. Ford

  DOI：10.1021/ic051824q

  日期：2006.5.1

  The heterogeneous reaction between NO gas and sublimed layers of manganese(II) porphyrinato complexes Mn(Por) (Por) TPP = tetraphenylporphyrinato dianion), TMP (tetramesitylporphyrinato dianion), or TPPd20 ( perdeuterated tetraphenylporphyrinato dianion)) has been monitored by IR and optical spectroscopy over the temperature range of 77 K to room temperature. These manganese porphyrins promote NO disproportionation to NO2 species and N2O, and the reaction proceeds via several distinct stages. At 90 K, the principal species observed spectrally are the nitric oxide dimer, cis-ONNO, two manganese nitrosyls, the simple NO adduct Mn( Por)(NO), and another intermediate (1) that is apparently critical to the disproportionation mechanism. This key intermediate is formed prior to N2O evolution, and proposals regarding its likely structure are offered. When the system is warmed to 130 K, the disproportionation products, N2O and the O-coordinated nitrito complex Mn( Por)(NO)(ONO) ( 2), are formed. IR spectral changes show that, upon further warming to 200 K, 2 isomerizes into the N-bonded nitro linkage isomer Mn(Por)(NO)(NO2) ( 3). After it is warmed to room temperature, the latter species loses NO and converts to the known 5-coordinate nitrito complex Mn(Por)(ONO) (4).