Quantification of sigma-acceptor and pi-donor stabilization in O, S and Hal analogues of N-heterocyclic carbenes (NHCs) on the magnetic criterion
- The spatial magnetic properties, through-space NMR shieldings (TSNMRSs), of stable O, S and Hal analogues of N-heterocyclic carbenes (NHCs) have been calculated using the GIAO perturbation method employing the nucleus-independent chemical shift (NICS) concept and the results visualized as iso-chemical-shielding surfaces (ICSSs) of various sizes and directions. The TSNMRS values (actually the anisotropy effects measurable in H-1 NMR spectroscopy) are employed to qualify and quantify the position of the present mesomeric equilibria (carbenes <-> ylides). The results are confirmed by geometry (bond angles and bond lengths), IR spectra, UV spectra, and C-13 chemical shifts of the electron-deficient carbon centers.
| Author details: | Erich KleinpeterORCiDGND, Andreas KochGND |
|---|---|
| DOI: | https://doi.org/10.1021/acs.jpca.1c05257 |
| ISSN: | 1089-5639 |
| ISSN: | 1520-5215 |
| Pubmed ID: | https://pubmed.ncbi.nlm.nih.gov/34387991 |
| Title of parent work (English): | The journal of physical chemistry : A, Molecules, spectroscopy, kinetics, environment & general theory |
| Publisher: | American Chemical Society |
| Place of publishing: | Washington |
| Publication type: | Article |
| Language: | English |
| Date of first publication: | 2021/08/13 |
| Publication year: | 2021 |
| Release date: | 2023/02/02 |
| Volume: | 125 |
| Issue: | 33 |
| Number of pages: | 11 |
| First page: | 7235 |
| Last Page: | 7245 |
| Organizational units: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie |
| DDC classification: | 5 Naturwissenschaften und Mathematik / 53 Physik / 530 Physik |
| 5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften | |
| Peer review: | Referiert |
