| Автор | Eckert-Maksić, Mirjana |
| Автор | Maskill, Howard |
| Автор | Zrinski, Irena |
| Дата выпуска | 2001 |
| dc.description | Deprotonation from nitrogen of the aci-nitro tautomer (4) of nitramide (1) has been shown to give an anion which does not correspond to an energy minimum on the potential energy surface. The base-catalysed decomposition of nitramide via this tautomer, therefore, occurs by an enforced concerted mechanism which, on the basis of previously reported experimental results, is deduced to be highly asynchronous. Protonation of 4 on the hydroxy also leads to an ion which spontaneously fragments, consequently the acid-catalysed decomposition of 1 via 4 also involves concerted proton transfer and fragmentation. The uncatalysed decomposition of nitramide through the same tautomer 4 is also concerted, and the mechanism through a cyclic transition structure involving two water molecules is shown to be more favourable than a cyclic concerted mechanism involving a single water molecule. Structures and energies of all relevant species have been calculated and shown to be in good agreement with experimental results where these are available. |
| Формат | application.pdf |
| Издатель | Royal Society of Chemistry |
| Название | Acidic and basic properties of nitramide, and the catalysed decomposition of nitramide and related compounds: an ab initio theoretical investigationElectronic supplementary information (ESI) available: selected geometrical parameters, energies and zero point energies of nitramide 1, its aci-nitro isomers 4a–d, anion 7, and molecular complexes MC1 and MC1′ calculated at MP2/6-31G** and MP2/6-311++G** levels of theory. See http://www.rsc.org/suppdata/p2/b1/b105074p/ |
| Тип | research-article |
| DOI | 10.1039/b105074p |
| Electronic ISSN | 1364-5471 |
| Print ISSN | 0300-9580 |
| Журнал | Journal of the Chemical Society, Perkin Transactions 2 |
| Первая страница | 2147 |
| Последняя страница | 2154 |
| Аффилиация | Eckert-MaksiÄ Mirjana; Department of Chemistry and Biochemistry, RuÄ er Bos.breve;koviÄ Institute |
| Аффилиация | Maskill Howard; Chemistry Department, University of Newcastle |
| Аффилиация | Zrinski Irena; Department of Chemistry and Biochemistry, RuÄ er Bos.breve;koviÄ Institute |
| Выпуск | 11 |
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