Mechanisms of HNO and NO production from Angeli's salt: density functional and CBS-QB3 theory predictions

Andrew S Dutton; Jon M Fukuto; K N Houk

doi:10.1021/ja0391614

Mechanisms of HNO and NO production from Angeli's salt: density functional and CBS-QB3 theory predictions

J Am Chem Soc. 2004 Mar 31;126(12):3795-800. doi: 10.1021/ja0391614.

Authors

Andrew S Dutton¹, Jon M Fukuto, K N Houk

Affiliation

¹ Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, USA.

PMID: 15038733
DOI: 10.1021/ja0391614

Abstract

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.

Publication types

Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, P.H.S.

MeSH terms

Models, Chemical
Models, Molecular
Molecular Structure
Nitric Oxide / chemistry*
Nitrites / chemistry*
Nitrogen Oxides / chemistry*
Thermodynamics

Substances

Nitrites
Nitrogen Oxides
oxyhyponitrite
Nitric Oxide
nitroxyl