1H chemical shifts in NMR. Part 27 : proton chemical shifts in sulfoxides and sulfones and the magnetic anisotropy, electric field and steric effects of the SO bond
Copyright (c) 2008 John Wiley & Sons, Ltd.
| Publié dans: | Magnetic resonance in chemistry : MRC. - 1985. - 46(2008), 7 vom: 28. Juli, Seite 667-75 |
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| Auteur principal: | |
| Autres auteurs: | , |
| Format: | Article en ligne |
| Langue: | English |
| Publié: |
2008
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| Accès à la collection: | Magnetic resonance in chemistry : MRC |
| Sujets: | Journal Article Research Support, Non-U.S. Gov't Protons Solutions Sulfones Sulfoxides |
| Résumé: | Copyright (c) 2008 John Wiley & Sons, Ltd. The (1)H chemical shifts of a series of sulfoxide and sulfone compounds in CDCl(3) solvent were obtained from experiment and the literature. These included dialkyl sulfoxides and sulfones (R(2)SO/R(2)SO(2), R = Me, Et, Pr, n-Bu), the cyclic compounds tetramethylene sulfoxide/sulfone, pentamethylene sulfoxide/sulfone and the aromatic compounds p-tolylmethylsulfoxide, dibenzothiopheneoxide/dioxide, E-9-phenanthrylmethylsulfoxide and (E) (Z)-1-methylsulfinyl-2-methylnaphthalene. The spectra of the pentamethylene SO and SO(2) compounds were obtained at -70 degrees C to obtain the spectra from the separate conformers (SO) and from the noninverting ring (SO(2)). This allowed the determination of the substituent chemical shifts (SCS) of the SO and SO(2) functional groups, which were analyzed in terms of the SO bond electric field, magnetic anisotropy and steric effect for long-range protons together with a model (CHARGE8d) for the calculation of the two and three bond effects. After parameterization, the overall root mean square (RMS) error (observed-calculated) for a dataset of 354 (1)H chemical shifts was 0.11 ppm. The anisotropy of the SO bond was found to be very small, supporting the dominant single bond S(+)--O(-) character of this bond |
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| Description: | Date Completed 05.08.2008 Date Revised 24.11.2016 published: Print Citation Status MEDLINE |
| ISSN: | 1097-458X |
| DOI: | 10.1002/mrc.2229 |