Push-pull allenes-conjugation, (anti)aromaticity and quantification of the push-pull character
- Structures, H-1/C-13 chemical shifts, and pi electron distribution/conjugation of an experimentally available and theoretically completed set of push-pull allenes Acc(2)C=C=CDon(2) (Acc=F, CHO, CF3, C N; Don=t-Bu, OMe, OEt, SMe, SEt, NCH2R) have been computed at the OFT level of theory. Both orthogonal linear and orthogonal bent structures have been obtained. In the latter case the push-pull character could be quantified by the quotient method. The C-13 chemical shift of the central allene carbon atom C-2 and chemical shift differences Delta delta(C-1, C-2) and Delta delta(C-2, C-3) of allene carbon atoms proved to be a quantitative alternative. TSNMRS of ring-closed push-pull allenes have been computed in addition and were employed to identify polar, carbene-like and carbone-like canonical structures of these molecules.
Verfasserangaben: | Erich KleinpeterORCiDGND, Peter Werner, Andreas KochORCiDGND |
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DOI: | https://doi.org/10.1016/j.tet.2013.01.027 |
ISSN: | 0040-4020 |
Titel des übergeordneten Werks (Englisch): | Tetrahedron |
Verlag: | Elsevier |
Verlagsort: | Oxford |
Publikationstyp: | Wissenschaftlicher Artikel |
Sprache: | Englisch |
Jahr der Erstveröffentlichung: | 2013 |
Erscheinungsjahr: | 2013 |
Datum der Freischaltung: | 26.03.2017 |
Freies Schlagwort / Tag: | Aromaticity; C-13 NMR spectroscopy; ICSS; Push-pull allenes; Push-pull character; Quotient method; TSNMRS |
Band: | 69 |
Ausgabe: | 11 |
Seitenanzahl: | 10 |
Erste Seite: | 2436 |
Letzte Seite: | 2445 |
Organisationseinheiten: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie |
Peer Review: | Referiert |