β-Phosphorus Hyperfine Coupling Constant in Nitroxides: Conformational Effects in 6-Membered Ring Nitroxides

Autor: Gigmes, Didier, Bosco, Lionel, Butscher, Teddy, Marque, Sylvain
Přispěvatelé: Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Physique des interactions ioniques et moléculaires (PIIM), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Institut Lavoisier de Versailles (ILV), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)
Jazyk: angličtina
Rok vydání: 2017
Předmět:
Zdroj: Applied Magnetic Resonance
Applied Magnetic Resonance, 2017, 48 (4), pp.379-406. ⟨10.1007/s00723-017-0867-z⟩
Applied Magnetic Resonance, Springer Verlag, 2017, 48 (4), pp.379-406. ⟨10.1007/s00723-017-0867-z⟩
ISSN: 0937-9347
1613-7507
DOI: 10.1007/s00723-017-0867-z⟩
Popis: Recently, we reported a significant solvent effect on the phosphorus hyperfine coupling constant a P in β-phosphorylated 6-membered ring nitroxides (∆a P = 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 a P with the polarity of solvent was still observed for these nitroxides. As for other β-phosphorylated nitroxides, a N increases with the polarity/polarizability π* and the Hydrogen Bond Donating α properties of the solvent whereas a P exhibits the reverse trends. The change of a P 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.
Databáze: OpenAIRE
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