Dutton Andrew S, Suhrada Christopher P, Miranda Katrina M, Wink David A, Fukuto Jon M, Houk K N
Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, USA.
Inorg Chem. 2006 Mar 20;45(6):2448-56. doi: 10.1021/ic051505z.
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.
异丙胺二氮烯二醇盐（IPA/NO）是异丙胺与一氧化氮（NO）反应的产物，它在pH值为13至高于5的范围内以pH依赖的方式分解生成硝酰（HNO），在pH值低于7时生成NO。使用B3LYP/6-311+G(d)密度泛函理论、极化连续介质和类导体极化连续介质溶剂化模型以及高精度CBS-QB3方法对简化模型化合物甲胺二氮烯二醇盐进行的理论研究预测了一种机制，即通过不稳定互变异构体MeNN+(O-)NHO-的分解产生HNO。预计在较低pH值下NO的产生是由于胺氮质子化后酰胺/NO加合物的碎片化。
