Mechanisms of HNO and NO production from Angeli's salt: density functional and CBS-QB3 theory predictions.
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.
Dutton
Andrew S
AS
Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, USA.
Fukuto
Jon M
JM
Houk
K N
KN
D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D009569:Nitric Oxide / Q000737:chemistry*; D009573:Nitrites / Q000737:chemistry*; D009589:Nitrogen Oxides / Q000737:chemistry*; D013816:Thermodynamics
D009573:Nitrites; D009589:Nitrogen Oxides; C021229:oxyhyponitrite; D009569:Nitric Oxide; C039900:nitroxyl