Stereochemical dependence of NMR geminal spin-spin coupling constants
2008 John Wiley & Sons, Ltd.
| Veröffentlicht in: | Magnetic resonance in chemistry : MRC. - 1985. - 47(2009), 2 vom: 30. Feb., Seite 113-20 |
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| Weitere Verfasser: | , , |
| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2009
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| Zugriff auf das übergeordnete Werk: | Magnetic resonance in chemistry : MRC |
| Schlagworte: | Journal Article |
| Zusammenfassung: | 2008 John Wiley & Sons, Ltd. In this work it was sought to explore the versatility of geminal spin-spin coupling constants, (2)J(XY) SSCCs, as probes for stereochemical studies. A set of compounds, where their experimental (2)J(XY) SSCCs through the X-C-Y molecular fragment are predicted to be sensitive to hyperconjugative interactions involving either bonding or antibonding orbitals containing the C carbon atom ('coupling pathway'), were analyzed. SSCC calculations were performed for some selected examples using the second order polarization propagator approximation (SOPPA) method or within the DFT-B3LYP framework. Hyperconjugative interactions were calculated within the Natural Bond Orbital (NBO) approach. Results are condensed in two qualitative rules: Rule I(M)-hyperconjugative interactions transferring charge into the coupling pathway yield a positive increase to the Fermi contact (FC), contribution to (2)K(XY) reduced spin-spin coupling constants (RSSCC), and Rule II(M)-hyperconjugative interactions transferring charge from the coupling pathway yield a negative increase to the FC contribution to (2)K(XY) RSSCC |
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| Beschreibung: | Date Completed 27.02.2009 Date Revised 12.01.2009 published: Print Citation Status PubMed-not-MEDLINE |
| ISSN: | 1097-458X |
| DOI: | 10.1002/mrc.2359 |