Trivinylphosphine and trivinylphosphine chalcogenides : stereochemical trends of ³¹P-¹H spin-spin coupling constants
Copyright © 2010 John Wiley & Sons, Ltd.
| Veröffentlicht in: | Magnetic resonance in chemistry : MRC. - 1985. - 48 Suppl 1(2010) vom: 25. Dez., Seite S48-55 |
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| 1. Verfasser: | |
| Weitere Verfasser: | , , , |
| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2010
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| Zugriff auf das übergeordnete Werk: | Magnetic resonance in chemistry : MRC |
| Schlagworte: | Journal Article Research Support, Non-U.S. Gov't Chalcogens Phosphorus Isotopes Protons Vinyl Compounds |
| Zusammenfassung: | Copyright © 2010 John Wiley & Sons, Ltd. A combined theoretical and experimental study of the stereochemical behavior of (31)P-(1)H spin-spin coupling constants has been performed in the series of trivinylphosphine and related trivinylphosphine oxide, sulfide and selenide. Theoretical energy-based conformational analysis of the title compounds performed at the MP2/6-311G** level reveals that each of the four compounds of this series exists in the equilibrium mixture of five true-minimum conformers, namely s-cis-s-cis-s-cis, s-cis-s-cis-gauche, syn-s-cis-gauche-gauche, anti-s-cis-gauche-gauche and gauche-gauche-gauche, which were taken into account in the conformational averaging of (31)P-(1)H spin-spin couplings calculated at the second-order polarization propagator approach/aug-cc-pVTZ-J level of theory. All (31)P-(1)H spin-spin coupling constants involving phosphorus and either of the vinyl protons are found to demonstrate a marked stereochemical dependences with respect to the geometry of the coupling pathway and internal rotation of the vinyl group around the P-C bond which is of major importance in the stereochemical studies of the unsaturated phosphines and phosphine chalcogenides |
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| Beschreibung: | Date Completed 22.03.2011 Date Revised 24.11.2010 published: Print Citation Status MEDLINE |
| ISSN: | 1097-458X |
| DOI: | 10.1002/mrc.2614 |