Mechanism of pH-dependent decomposition of monoalkylamine diazeniumdiolates to form HNO and NO, deduced from the model compound methylamine diazeniumdiolate, density functional theory, and CBS-QB3 calculations

Andrew S. Dutton, Christopher P. Suhrada, Katrins M. Miranda, David A. Wink, Jon M. Fukuto, K. N. Houk

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Isopropylamine diazeniumdiolate, IPA/NO, the product of the reaction of isopropylamine and nitric oxide, NO, decomposes in a pH-dependent manner to afford nitroxyl, HNO, in the pH range of 13 to above 5, and NO below pH 7. Theoretical studies using B3LYP/6-311+G(d) density functional theory, the polarizable continuum and conductor-like polarizable continuum solvation models, and the high-accuracy CBS-QB3 method on the simplified model compound methylamine diazeniumdiolate predict a mechanism involving HNO production via decomposition of the unstable tautomer MeNN+(O-)NHO -. The production of NO at lower pH is predicted to result from fragmentation of the amide/NO adduct upon protonation of the amine nitrogen.

Original languageEnglish (US)
Pages (from-to)2448-2456
Number of pages9
JournalInorganic Chemistry
Issue number6
StatePublished - Mar 20 2006


ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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