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.
| Author details: | Erich KleinpeterORCiDGND, Ute Klaumuenzer |
|---|---|
| DOI: | https://doi.org/10.1016/j.molstruc.2014.05.072 |
| ISSN: | 0022-2860 |
| ISSN: | 1872-8014 |
| Title of parent work (English): | Journal of molecular structure |
| Publisher: | Elsevier |
| Place of publishing: | Amsterdam |
| Publication type: | Article |
| Language: | English |
| Year of first publication: | 2014 |
| Publication year: | 2014 |
| Release date: | 2017/03/27 |
| Tag: | C-13 chemical shift difference Delta delta(C C); Occupation quotient pi*/pi; Push-pull alkynes; Push-pull effect; Steric hindrance |
| Volume: | 1074 |
| Number of pages: | 3 |
| First page: | 193 |
| Last Page: | 195 |
| Organizational units: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie |
| Peer review: | Referiert |
