trioxodinitrate anion | 15435-67-3

• 分子结构分类: 无机化合物 - 均质非金属化合物 - 其他非金属有机物
• 英文名称: trioxodinitrate anion
• 英文别名: trioxodinitrate (2-)；trioxodinitrate(II)(2-)；oxyhyponitrate(2-)；trioxido-1kappa(2)O,2kappaO-dinitrate(N--N)(2-)；N,N-dioxidonitrous amide
• CAS: 15435-67-3
• 化学式: N₂O₃
• 分子量: 76.0116
• InChiKey: NDJGQNJPALSQEN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1
• 重原子数：
  5
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  78.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  trioxodinitrate anion 在 acid 作用下， 以 not given 为溶剂， 生成 氧化亚氮
  参考文献：
  名称：

  Angeli, A., Chemiker-Zeitung, 1896, vol. 20, p. 176

  摘要：

  DOI：

文献信息

• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Ni: MVol.B3, 63, page 905 - 907
  作者：

  DOI：——

  日期：——
• Angeli, A., Gazzetta Chimica Italiana, 1897, vol. 27 II, p. 365
  作者：Angeli, A.

  DOI：——

  日期：——
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: N: MVol.4, 3, page 870 - 872
  作者：

  DOI：——

  日期：——
• Angeli, A., Gazzetta Chimica Italiana, 1896, vol. 26 II, p. 20
  作者：Angeli, A.

  DOI：——

  日期：——
• Spin-Forbidden Deprotonation of Aqueous Nitroxyl (HNO)
  作者：Vladimir Shafirovich、Sergei V. Lymar

  DOI：10.1021/ja034378j

  日期：2003.5.1

  The first mechanistic study of a spin-forbidden proton-transfer reaction in aqueous solution is reported. Laser flash photolysis of alkaline trioxodinitrate (N2O32-, Angeli's anion) is used to generate a nitroxyl anion in its excited singlet state ((NO-)-N-1). Through rapid partitioning between protonation by water and electronic relaxation, (NO-)-N-1 produces (HNO)-H-1 (ground state, yield 96%) and (NO-)-N-3 (ground state, yield 4%), which comprise a unique conjugate acid-base couple with different ground-state multiplicities. Using the large difference between reactivities of (HNO)-H-1 and (NO-)-N-3 in the peroxynitrite-forming reaction with 3 02, the kinetics of spin-forbidden deprotonation reaction (HNO)-H-1 + OH- --> (NO-)-N-3 + H2O is investigated in H2O and D2O. Consistent with proton transfer, this reaction exhibits primary kinetic hydrogen isotope effect k(H)/k(D) = 3.1 at 298 K, which is found to be temperature-dependent. Arrhenius pre-exponential factors and activation energies of the second-order rate constant are found to be: log(A, M-1 s(-1)) = 10.0 +/- 0.2 and E-a = 30.0 +/- 1.1 kJ/mol for proton transfer and log(A, M-1 s(-1)) = 10.4 +/- 0.1 and E-a = 35.1 +/- 0.7 kJ/mol for deuteron transfer. Collectively, these data are interpreted to show that the nuclear reorganization requirements arising from the spin prohibition necessitate significant activation before spin change can take place, but the spin change itself must occur extremely rapidly. It is concluded that a synergy between the spin prohibition and the reaction energetics creates an intersystem barrier and is responsible for slowness of the spin-forbidden deprotonation of (HNO)-H-1 by OH-; the spin prohibition alone plays a minor role.