title: Photoinduced release of nitroxyl and nitric oxide from diazeniumdiolates.
abstract: Aqueous photochemistry of diazen-1-ium-1,2,2-triolate (Angeli's anion) and (Z)-1[N-(3-aminopropyl)-N-(3-aminopropyl)amino]diazen-1-ium-1,2-diolate (DPTA NONOate) has been investigated by laser kinetic spectroscopy. In neutral aqueous solutions, 266 nm photolysis of these diazeniumdiolates generates a unique spectrum of primary products including the ground-state triplet (3NO-) and singlet (1HNO) nitroxyl species and nitric oxide (NO*). Formation of these spectrophotometrically invisible products is revealed and quantitatively assayed by analyzing a complex set of their cross-reactions leading to the formation of colored intermediates, the N2O2*- radical and N3O3- anion. The experimental design employed takes advantage of the extremely slow spin-forbidden protic equilibration between 3NO- and 1HNO and the vast difference in their reactivity toward NO*. To account for the kinetic data, a novel combination reaction, 3NO-+1HNO, is introduced, and its rate constant of 6.6x10(9) M-1 s-1 is measured by competition with the reduction of methyl viologen by 3NO-. The latter reaction occurring with 2.1x10(9) M-1 s-1 rate constant and leading to the stable, colored methyl viologen radical cation is useful for detection of 3NO-. The distributions of the primary photolysis products (Angeli's anion: 22% 3NO-, 58% 1HNO, and 20% NO*; DPTA NONOate: 3% 3NO-, 12% 1HNO, and 85% NO*) show that neither diazeniumdiolate is a highly selective photochemical generator of nitroxyl species or nitric oxide, although the selectivity of DPTA NONOate for NO* generation is clearly greater.
authors.affiliation: Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973, USA.
authors.forename: Sergei V
authors.initials: SV
authors.lastname: Lymar
authors.forename: Vladimir
authors.initials: V
authors.lastname: Shafirovich
mesh_terms: D001391:Azo Compounds / Q000737:chemistry*; D007834:Lasers; D009569:Nitric Oxide / Q000737:chemistry*; D009589:Nitrogen Oxides / Q000737:chemistry*; D010782:Photolysis; D012996:Solutions; D014466:Ultraviolet Rays
chemical_list: D001391:Azo Compounds; D009589:Nitrogen Oxides; D012996:Solutions; C452539:diazeniumdiolate; D009569:Nitric Oxide; C039900:nitroxyl