The mechanism of NO formation from the decomposition of dialkylamino diazeniumdiolates: Density functional theory and CBS-QBS predictions

被引：40

作者：

Dutton, AS

Fukuto, JM

Houk, KN ^{[1
]}

机构：

[1] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA

[2] Univ Calif Los Angeles, Sch Med, Dept Pharmacol, Los Angeles, CA 90095 USA

来源：

INORGANIC CHEMISTRY | 2004年 / 43卷 / 03期

关键词：

D O I：

10.1021/ic0349609

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The mechanism of decomposition of dialkylamino diazeniumdiolate salts, R2N[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.

引用

页码：1039 / 1045

页数：7

共 49 条

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