nitrous-15N-18O2 acid | 33753-89-8

• 英文名称: nitrous-15N-18O2 acid
• CAS: 33753-89-8
• 化学式: NO₂
• 分子量: 51.0
• InChiKey: JCXJVPUVTGWSNB-UKEFCNGDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  3.0
• 可旋转键数：
  0.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  49.33
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  nitrous-15N-18O2 acid 、 2,3,5,7-四苯基-21H,23H-卟吩锰(2+)盐(1:1) 以 neat (no solvent) 为溶剂， 生成 Mn(meso-tetraphenylporphyrinatodianion)(η1-¹⁸O¹⁵N¹⁸O)
  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