期刊
DALTON TRANSACTIONS
卷 41, 期 45, 页码 13779-13787出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c2dt31526b
关键词
-
资金
- Swiss National Fonds
- ETH Zurich
The isomerisation of ONOOH to NO3- and H+, some oxidations and all hydroxylations and nitrations of aromatic compounds are first-order in ONOOH and zero-order in the compounds that are modified. These reactions are widely believed to proceed via homolysis of ONOOH into HO center dot and NO2 center dot to an extent of ca. 30%. We review the evidence pro and contra homolysis in studies that involve (1) thermochemical considerations, (2) isomerisation to NO3- and H+, (3) decomposition to NO2- and O-2, (4) HO center dot scavenger studies, (5) deuterium isotope effects, (6) O-18-scrambling studies, (7) electrochemistry, (8) CIDNP NMR, and (9) photolysis. Our conclusion is that homolysis may be involved to a minor extent of ca. 5%. The initiation of ONOOH isomerisation may be visualised as an out-of-plane vibration of the terminal HO-group relative to the nitrogen. At ONOO- concentrations exceeding 0.1 mM and near neutral pH, disproportionation to NO2- and O-2 occurs; such disproportionations are typical for peroxy acids. For oxidation and nitration of organic substrates, we favour a mechanism involving initial formation of an adduct between the compound to be oxidised or nitrated and ONOOH.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据