Aminoxyl (Nitroxyl) Radicals in the Early Decomposition of the Nitramine RDX

详细信息    查看全文

• 作者：Karl K. Irikura
• 刊名：The Journal of Physical Chemistry A
• 出版年：2013
• 出版时间：March 14, 2013
• 年：2013
• 卷：117
• 期：10
• 页码：2233-2241
• 全文大小：450K
• 年卷期：v.117,no.10(March 14, 2013)
• ISSN：1520-5215

文摘

The explosive nitramine RDX (1,3,5-trinitrohexahydro-s-triazine) is thought to decompose largely by homolytic N鈥揘 bond cleavage, among other possible initiation reactions. Density-functional theory (DFT) calculations indicate that the resulting secondary aminyl (R₂N路) radical can abstract an oxygen atom from NO₂ or from a neighboring nitramine molecule, producing an aminoxyl (R₂NO路) radical. Persistent aminoxyl radicals have been detected in electron-spin resonance (ESR) experiments and are consistent with autocatalytic 鈥渞ed oils鈥?reported in the experimental literature. When the O-atom donor is a nitramine, a nitrosamine is formed along with the aminoxyl radical. Reactions of aminoxyl radicals can lead readily to the 鈥渙xy-s-triazine鈥?product (as the s-triazine N-oxide) observed mass-spectrometrically by Behrens and co-workers. In addition to forming aminoxyl radicals, the initial aminyl radical can catalyze loss of HONO from RDX.