title: The mechanism of NO formation from the decomposition of dialkylamino diazeniumdiolates: density functional theory and CBS-QB3 predictions.
abstract: The mechanism of decomposition of dialkylamino diazeniumdiolate salts, R(2)N[NONO](-)M(+), to form nitric oxide, NO, was explored using theoretical methods. B3LYP/6-311+G(d) density functional theory calculations gave the optimized geometries, and energetics were further evaluated with the high accuracy CBS-QB3 method, when feasible. Relative pK(a) values were estimated using the PCM model for aqueous solvation. The terminal oxygen is the most basic site, followed closely by the internal oxygen. Protonation of these sites does not lead to decomposition. However, protonation of the weakly basic amino nitrogen leads to very rapid decomposition and NO generation.
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, USA.
authors.forename: Andrew S
authors.initials: AS
authors.lastname: Dutton
authors.forename: Jon M
authors.initials: JM
authors.lastname: Fukuto
authors.forename: K N
authors.initials: KN
authors.lastname: Houk
mesh_terms: D000465:Algorithms; D000473:Alkanes / Q000737:chemistry*; D001391:Azo Compounds / Q000737:chemistry*; D004563:Electrochemistry; D007202:Indicators and Reagents; D007700:Kinetics; D008956:Models, Chemical; D009569:Nitric Oxide / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry; D012995:Solubility; D013816:Thermodynamics
chemical_list: D000473:Alkanes; D001391:Azo Compounds; D007202:Indicators and Reagents; D009569:Nitric Oxide; D010100:Oxygen