Z,E-isomerization mechanism for N-arylthio-1,4-benzoquinonimines : DNMR and DFT investigations
2008 John Wiley & Sons, Ltd.
| Veröffentlicht in: | Magnetic resonance in chemistry : MRC. - 1985. - 46(2008), 9 vom: 05. Sept., Seite 811-7 |
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| Weitere Verfasser: | , , , |
| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2008
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| Zugriff auf das übergeordnete Werk: | Magnetic resonance in chemistry : MRC |
| Schlagworte: | Journal Article Research Support, Non-U.S. Gov't Benzoquinones Imines Sulfhydryl Compounds |
| Zusammenfassung: | 2008 John Wiley & Sons, Ltd. Z,E-isomerization has been investigated for the series of the N-arylthio-1,4-benzoquinonimines using a line shape analysis in the (1)H NMR spectra. Thermodynamic parameters and substituent effects have been analyzed for the isomerization process. It has been shown based on the DFT (B3LYP) calculations that the dynamic transformation for N-arylthio-1,4-benzoquinonimines should be considered as a combination of the two different processes, a rotation about the N-S bond and an inversion at nitrogen via the transition state with the linear C=N-S moiety. The free energies of activation for the isomerization (DeltaG(298 K)) measured experimentally depend on the substitution in the quinonimine moiety and phenyl ring and can be referred either to the inversion of the nitrogen atom or to the hindered rotation about the N-S bond |
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| Beschreibung: | Date Completed 30.10.2008 Date Revised 11.08.2008 published: Print Citation Status MEDLINE |
| ISSN: | 1097-458X |
| DOI: | 10.1002/mrc.2254 |