Dutton Andrew S, Fukuto Jon M, Houk K N
Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, USA.
J Am Chem Soc. 2004 Mar 31;126(12):3795-800. doi: 10.1021/ja0391614.
The mechanism of decomposition of Angeli's salt, Na(2)N(2)O(3), was explored with B3LYP and CBS-QB3 computational methods. Angeli's salt produces both nitroxyl (HNO) and nitric oxide (NO), depending upon the pH of the solution. These calculations show that protonation on N(2), while less favorable than O protonation, leads spontaneously to HNO production, while diprotonation at O(3) leads to NO generation. K(a) values for protonation at different centers and rate constants have been found which reproduce experimental data satisfactorily.
采用B3LYP和CBS-QB3计算方法探究了安吉利盐（Na₂N₂O₃）的分解机制。根据溶液的pH值，安吉利盐会生成硝酰（HNO）和一氧化氮（NO）。这些计算表明，N₂上的质子化虽然不如O质子化有利，但会自发产生HNO，而O₃处的双质子化会导致NO生成。已得出不同中心质子化的Kₐ值和速率常数，它们令人满意地重现了实验数据。
