Comparative study of structure and photo-induced reactivity of malonaldehyde and acetylacetone isolated in nitrogen matrices
Structure and reactivity of the eight enolic forms (one chelated and seven non-chelated) of malonaldehyde and acetylacetone are compared through theoretical and experimental data. Ground-state geometries, energies, and vibrational frequencies are calculated with the B3LYP/6–311++G(2d,2p) model ch...
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| Datum: | 2006 |
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| Hauptverfasser: | , , , , , |
| Format: | Artikel |
| Sprache: | English |
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Фізико-технічний інститут низьких температур ім. Б.І. Вєркіна НАН України
2006
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| Schriftenreihe: | Физика низких температур |
| Schlagworte: | |
| Online Zugang: | http://dspace.nbuv.gov.ua/handle/123456789/120884 |
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| Назва журналу: | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| Zitieren: | Comparative study of structure and photo-induced reactivity of malonaldehyde and acetylacetone isolated in nitrogen matrices / A. Trivella, S. Coussan, T. Chiavassa, P. Theule, C. Manca, P. Roubin // Физика низких температур. — 2006. — Т. 32, № 11. — С. 1372–1381. — Бібліогр.: 59 назв. — англ. |
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Digital Library of Periodicals of National Academy of Sciences of Ukraine| Zusammenfassung: | Structure and reactivity of the eight enolic forms (one chelated and seven non-chelated) of
malonaldehyde and acetylacetone are compared through theoretical and experimental data.
Ground-state geometries, energies, and vibrational frequencies are calculated with the
B3LYP/6–311++G(2d,2p) model chemistry. The electronic delocalisation as well as the
cis/trans rotamer properties are analysed. The hydrogen bond strength of the chelated forms can
be estimated by the energy difference between chelated and non-chelated forms, and its enhancement
due to methyl-induced electron release is estimated at 1.7 kcal·mol⁻¹. UV- and
IR-induced reactivity of molecules isolated in nitrogen matrices is studied by means of FT–IR
spectrometry. Interconversion between rotamers is the main process observed for both molecules,
only some among the seven non-chelated forms being created. |
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