The β-phosphorus hyperfine coupling constant in nitroxide: part 3: titration of water by electron paramagnetic resonance

Audran, Gérard; Bosco, Lionel; Brémond, Paul; Butscher, Teddy; Franconi, Jean‐Michel; Marque, Sylvain R. A.; Mellet, Philippe; Parzy, Elodie; Santelli, Maurice; Thiaudière, Eric

doi:10.1039/c5ob01867f

Cited by 5 publications

(19 citation statements)

References 29 publications

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“…According to previous results, correlations performed by using non‐specific solvent properties afforded only shotgun like plots (not shown).…”

Section: Resultssupporting

confidence: 67%

“…The nitroxides displayed in Figure show the expected six‐line pattern in their EPR spectra . Signals were recorded in 44 solvents (Table ).…”

Section: Resultsmentioning

confidence: 92%

“…Recently, several solvent effect studies have been reported for β‐phosphorylated nitroxides and, although the trends are sometimes very different, the driving interaction governing the changes in a N and in a P is the same for all nitroxides. That is, for a N the driving interaction relies on the polarity/polarizability and HBD properties of the solvent, favoring form B (Figure ) and, hence, an increase in a N .…”

Section: Discussionmentioning

confidence: 99%

“… and 2 . until our recent reports . As all applications aforementioned depend dramatically on the changes in a N and a P , extensive investigations into solvent effects in this family of nitroxides are due.…”

Section: Introductionmentioning

confidence: 99%

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Intramolecular Hydrogen Bond Reverting the Solvent Effect on Phosphorus Hyperfine Coupling Constants of β‐Phosphorylated Nitroxides

et al. 2016

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Recently, we reported a dramatic solvent effect on the phosphorus hyperfine coupling constant a of β-phosphorylated six-membered ring nitroxides, that is, approximately 25 G of difference in a from n-hexane to water (Org. Biomol. Chem. 2016, 14, -1228-1292). In this article, we report on the effect of intramolecular hydrogen bonding (IHB) in three nitroxides exhibiting IHB between the hydroxyl and diethylphosphoryl groups and one exhibiting IHB between the hydroxyl group and the nitroxyl moiety. It is observed that for the first three nitroxides, a increases with increasing polarity/polarizability and hydrogen bond donor (HBD) properties of the solvent (π* and α, respectively)-in sharp contrast to the data reported in the literature-and for the last nitroxide, a decreases with π* and α. In fact, the occurrence of IHB induces a large strain, its suppression by hydrogen bond acceptor (HBA) solvents affords an increase in a .

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“…According to previous results, correlations performed by using non‐specific solvent properties afforded only shotgun like plots (not shown).…”

Section: Resultssupporting

confidence: 67%

“…The nitroxides displayed in Figure show the expected six‐line pattern in their EPR spectra . Signals were recorded in 44 solvents (Table ).…”

Section: Resultsmentioning

confidence: 92%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Intramolecular Hydrogen Bond Reverting the Solvent Effect on Phosphorus Hyperfine Coupling Constants of β‐Phosphorylated Nitroxides

et al. 2016

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“…Besides the absolute values of the coefficients of the KP and KAT relationships which describe the impact of each effect, the relative distribution given by their weight (w in %, eqn (18) and (19)) provides information on their relative *** However, for 4cc and 6cc, the HBD a parameter might be replaced by c, affording better correlations (see Table 5SI †), e.g., for 6cc (Fig. 5SI †).…”

Section: Multiparameter Correlationsmentioning

confidence: 99%

β-Phosphorus hyperfine coupling constant in nitroxides: 5. Solvent effect

et al. 2016

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Solvent effect in β-phosphorylated nitroxides. Part 4: detection of traces of water by electron paramagnetic resonance

et al. 2016

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For decades, the nitrogene hyperfine coupling constant aN of nitroxides has been applied to probe their environment using EPR. However, the small changes observed (≈2 G from n-pentane to water) with the solvent polarity allow only a qualitative discussion. A stable β-phosphorylated nitroxide exhibiting a small change in aN (≈3 G from n-pentane to water) and a striking change (≈25 G from n-pentane to water) in phosphorus hyperfine coupling constant aP with the polarity of solvent was prepared and used to develop the first procedure for the titration of water in THF by EPR, down to 0.1% v/v.

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The β-phosphorus hyperfine coupling constant in nitroxide: part 3: titration of water by electron paramagnetic resonance

Cited by 5 publications

References 29 publications

Intramolecular Hydrogen Bond Reverting the Solvent Effect on Phosphorus Hyperfine Coupling Constants of β‐Phosphorylated Nitroxides

Intramolecular Hydrogen Bond Reverting the Solvent Effect on Phosphorus Hyperfine Coupling Constants of β‐Phosphorylated Nitroxides

β-Phosphorus hyperfine coupling constant in nitroxides: 5. Solvent effect

Solvent effect in β-phosphorylated nitroxides. Part 4: detection of traces of water by electron paramagnetic resonance

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