β-Phosphorus Hyperfine Coupling Constant in Nitroxides: Conformational Effects in 6-Membered Ring Nitroxides
- Autores: Bosco L.1, Butscher T.1, Marque S.1,2
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Afiliações:
- Aix-Marseille Université, CNRS-UMR 7273, ICR
- N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS
- Edição: Volume 48, Nº 4 (2017)
- Páginas: 379-406
- Seção: Original Paper
- URL: https://journals.rcsi.science/0937-9347/article/view/247670
- DOI: https://doi.org/10.1007/s00723-017-0867-z
- ID: 247670
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Resumo
Recently, we reported a significant solvent effect on the phosphorus hyperfine coupling constant aP in β-phosphorylated 6-membered ring nitroxides (∆aP = 24 G in Org. Biomol. Chem. 2015). Thus, it led us to investigate the effect of solvent for several 6-membered ring nitroxides. Although smaller than mentioned above, a change of 5–7 G in aP with the polarity of solvent was still observed for these nitroxides. As for other β-phosphorylated nitroxides, aN increases with the polarity/polarizability π* and the Hydrogen Bond Donating α properties of the solvent whereas aP exhibits the reverse trends. The change of aP with the solvent depends a lot on a subtle interplay between the destabilizing steric hindrance due to the bulkiness of the substituents and the stabilizing hyperconjugation interactions SOMO → σ*C–P between the anti-bonding orbitals of the C–P bond and the SOMO.
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Sobre autores
Lionel Bosco
Aix-Marseille Université, CNRS-UMR 7273, ICR
Email: sylvain.marque@univ-amu.fr
França, Case 551, Avenue Escadrille Normandie-Niemen, Marseille Cedex 20, 13397
Teddy Butscher
Aix-Marseille Université, CNRS-UMR 7273, ICR
Email: sylvain.marque@univ-amu.fr
França, Case 551, Avenue Escadrille Normandie-Niemen, Marseille Cedex 20, 13397
Sylvain Marque
Aix-Marseille Université, CNRS-UMR 7273, ICR; N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS
Autor responsável pela correspondência
Email: sylvain.marque@univ-amu.fr
França, Case 551, Avenue Escadrille Normandie-Niemen, Marseille Cedex 20, 13397; Pr. Lavrentjeva 9, Novosibirsk, 630090