Quantification of the push-pull Effect in disubstituted alkynes - Application of occupation quotients pi*/pi and C-13 chemical shift differences Delta delta(C C)
- Structures, C-13 chemical shifts, and the occupation quotients of anti-bonding pi* and bonding pi orbitals of the C C triple bond along a series of push-pull alkynes (p)X-C6H4 C(O)-C C-NH-C6H4-Y(P) (X,Y= H, Me, OMe, NMe2, NO2, COMe, COOMe, F, Cl, Br) were computed at the DFT level (B3LYP/6-311G**) of theory. Both the stereochemistry (cis/trans-isomers) by steric twist and the push-pull character by both C-13 chemical shift differences (Delta delta(C C)) and the occupation quotient (pi(C C)/pi(C C)) were studied; the latter two parameters can be readily employed to precisely quantify the push-pull effect in alkynes. (C) 2014 Elsevier B.V. All rights reserved.
Verfasserangaben: | Erich KleinpeterORCiDGND, Ute Klaumuenzer |
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DOI: | https://doi.org/10.1016/j.molstruc.2014.05.072 |
ISSN: | 0022-2860 |
ISSN: | 1872-8014 |
Titel des übergeordneten Werks (Englisch): | Journal of molecular structure |
Verlag: | Elsevier |
Verlagsort: | Amsterdam |
Publikationstyp: | Wissenschaftlicher Artikel |
Sprache: | Englisch |
Jahr der Erstveröffentlichung: | 2014 |
Erscheinungsjahr: | 2014 |
Datum der Freischaltung: | 27.03.2017 |
Freies Schlagwort / Tag: | C-13 chemical shift difference Delta delta(C C); Occupation quotient pi*/pi; Push-pull alkynes; Push-pull effect; Steric hindrance |
Band: | 1074 |
Seitenanzahl: | 3 |
Erste Seite: | 193 |
Letzte Seite: | 195 |
Organisationseinheiten: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie |
Peer Review: | Referiert |