Open AccessOn the acidity and reactivity of HNO in aqueous solution and biological systems
Author(s) -
Michael D. Bartberger,
Jon M. Fukuto,
K. N. Houk
Publication year - 2001
Publication title -
proceedings of the national academy of sciences
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.011
H-Index - 771
eISSN - 1091-6490
pISSN - 0027-8424
DOI - 10.1073/pnas.041481598
Subject(s) - chemistry , nitroxyl , solvation , radiolysis , reactivity (psychology) , aqueous solution , thermochemistry , nucleophile , nitric acid , density functional theory , inorganic chemistry , computational chemistry , photochemistry , organic chemistry , molecule , medicine , alternative medicine , pathology , catalysis
The gas phase and aqueous thermochemistry and reactivity of nitroxyl (nitrosyl hydride, HNO) were elucidated with multiconfigurational self-consistent field and hybrid density functional theory calculations and continuum solvation methods. The pK(a) of HNO is predicted to be 7.2 +/- 1.0, considerably different from the value of 4.7 reported from pulse radiolysis experiments. The ground-state triplet nature of NO(-) affects the rates of acid-base chemistry of the HNO/NO(-) couple. HNO is highly reactive toward dimerization and addition of soft nucleophiles but is predicted to undergo negligible hydration (K(eq) = 6.9 x 10(-5)). HNO is predicted to exist as a discrete species in solution and is a viable participant in the chemical biology of nitric oxide and derivatives.
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