p-dinitrobenzene-d4 | 848223-49-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: p-dinitrobenzene-d4
• CAS: 848223-49-4
• 化学式: C₆H₄N₂O₄
• 分子量: 172.077
• InChiKey: FYFDQJRXFWGIBS-RHQRLBAQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  12.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  86.28
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  18-冠醚-6 、 p-dinitrobenzene-d4 在 氢化钾 作用下， 以 四氢呋喃 为溶剂， 生成 C₁₂H₂₄O₆*C₆⁽²⁾H₄N₂O₄^(1-)*K⁽¹⁺⁾
  参考文献：
  名称：

  “Separated” versus “Contact” Ion-Pair Structures in Solution from Their Crystalline States:  Dynamic Effects on Dinitrobenzenide as a Mixed-Valence Anion

  摘要：

  Qualitative structural concepts about dynamic ion pairs, historically deduced in solution as labile solvent-separated and contact species, are now quantified by the low-temperature isolation of crystalline (reactive) salts suitable for direct X-ray analysis. Thus, dinitrobenzenide anion (DNB-) can be prepared in the two basic ion-paired forms by potassium-mirror reduction of p-dinitrobenzene in the presence of macrocyclic polyether ligands: L-C (cryptand) and L-E (crown-ethers). The crystalline "separated" ion-pair salt isolated as K(L-C)(+)//DNB- is crystallographically differentiated from the "contact" ion-pair salt isolated as K(L-E)(DNB-)-D-divided by by their distinctive interionic separations. Spectral analysis reveals pronounced near-IR absorptions arising from intervalence transitions that characterize dinitrobenzenide to be a prototypical mixed-valence anion. Most importantly, the unique patterns of vibronic (fine-structure) progressions that also distinguish the "separated" from the "contact" ion pair in the crystalline solid state are the same as those dissolved into THF solvent and ensure that the same X-ray structures persist in solution. Moreover, these distinctive NIR patterns are assigned with the aid of Marcus-Hush (two-state) theory to the "separated" ion pair in which the unpaired electron is equally delocalized between both NO2-centers in the symmetric ground state of dinitrobenzenide, and by contrast, the asymmetric electron distribution inherent to "contact" ion pairs favors only that single NO2-center intimately paired to the counterion. The labilities of these dynamic ion pairs in solution are thoroughly elucidated by temperature-dependent ESR spectral changes that provide intimate details of facile isomerizations, ionic separations, and counterion-mediated exchanges.

  DOI：

  10.1021/ja043998x
• 作为产物：
  描述：

  硝基苯-d5 以40%的产率得到p-dinitrobenzene-d4
  参考文献：
  名称：

  “Separated” versus “Contact” Ion-Pair Structures in Solution from Their Crystalline States:  Dynamic Effects on Dinitrobenzenide as a Mixed-Valence Anion

  摘要：

  Qualitative structural concepts about dynamic ion pairs, historically deduced in solution as labile solvent-separated and contact species, are now quantified by the low-temperature isolation of crystalline (reactive) salts suitable for direct X-ray analysis. Thus, dinitrobenzenide anion (DNB-) can be prepared in the two basic ion-paired forms by potassium-mirror reduction of p-dinitrobenzene in the presence of macrocyclic polyether ligands: L-C (cryptand) and L-E (crown-ethers). The crystalline "separated" ion-pair salt isolated as K(L-C)(+)//DNB- is crystallographically differentiated from the "contact" ion-pair salt isolated as K(L-E)(DNB-)-D-divided by by their distinctive interionic separations. Spectral analysis reveals pronounced near-IR absorptions arising from intervalence transitions that characterize dinitrobenzenide to be a prototypical mixed-valence anion. Most importantly, the unique patterns of vibronic (fine-structure) progressions that also distinguish the "separated" from the "contact" ion pair in the crystalline solid state are the same as those dissolved into THF solvent and ensure that the same X-ray structures persist in solution. Moreover, these distinctive NIR patterns are assigned with the aid of Marcus-Hush (two-state) theory to the "separated" ion pair in which the unpaired electron is equally delocalized between both NO2-centers in the symmetric ground state of dinitrobenzenide, and by contrast, the asymmetric electron distribution inherent to "contact" ion pairs favors only that single NO2-center intimately paired to the counterion. The labilities of these dynamic ion pairs in solution are thoroughly elucidated by temperature-dependent ESR spectral changes that provide intimate details of facile isomerizations, ionic separations, and counterion-mediated exchanges.

  DOI：

  10.1021/ja043998x