Work

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

Year: 2006

Type: article

Abstract: 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.

Source: Inorganic Chemistry

DOI: 10.1021/ic051505z

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

Institutions: University of Arizona, University of California, Los Angeles, National Cancer Institute

Language: English

Topic: Chemical Reaction Mechanisms

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funder: National Institute of General Medical Sciences

Award: Theory of the Chemistry of NO, HNO, OONO-, and RSNO