Abstract
Solvent effects have been investigated for the last four decades. As far as we know, only 3 articles have reported on the solvent effect with β-phosphorylated nitroxides. In 1976, Il’Yasov and coll. (Theor Exp Chem 12:656, 1976) showed in 16 solvents that the phosphorus hyperfine coupling constant a P linearly decreased with the polarity of the solvent given by the normalized Reichardt–Dimroth polarity constant E TN for in situ generated nitroxides, e.g., from a P = 40.80 G in n-hexane (E NT = 0.09) to a P = 22.80 G in water (E NT = 1). A few years later, Janzen and coll. (Magn Reson Chem 37:251–258, 1999) reported a weak (around 4 G) decrease in a P for a few β-phosphorylated nitroxides in n-hexane and methanol. Recently, our group reported hardly any change in a P with the solvent for a very stable nitroxide, e.g., a P = 46.19 in n-pentane and a P = 45.60 in water. In this article, we report the solvent effect in 40 solvents on two new nitroxides and discuss at the light of the results reported in the literature. It turns out that a P changes obey no trends, i.e., strong or weak decrease, no change or even a weak increase in a P was observed depending on the structure of each nitroxide.
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Notes
The term B 0 in Eq. (2) corresponds to the coupling due to the spin polarization through the bond. In general, this term is small enough to be disregarded.
E NT is a composite parameter from polarity/polarizability π* and HBD α properties of the solvent.
References
B. Knauer, J.J. Napier, J. Am. Chem. Soc. 98, 4395–4400 (1976)
C. Reichardt, T. Welton, Solvent and Solvent Effect in Organic Chemistry, 4th edn. (Wiley, Weinheim, 2011)
Y. Marcus, The Properties of Solvents, Vol. 4 (Wiley, Chichester, 1998)
A. Sh. Mukhtarov, A. V. Il’Yasov, Ya. A. Levin, I. P. Gozman, M. S. Skorobogatova, E. I. Zoroatskaya, Theor. Exp. Chem. 12, 656–660 (1976); Teor. Eksp. Khim. 12, 831–836 (1976)
E.G. Janzen, G.A. Coulter, U.M. Oehler, J.P. Bergsma, Can. J. Chem. 60, 2725–2733 (1982)
D.L. Haire, E.G. Janzen, G. Chen, V.J. Robinson, I. Hrvoic, Magn. Reson. Chem. 37, 251–258 (1999)
C.-H. Deng, C.-J. Guan, M.-H. Shen, C.-X. Zhao, J. Fluorine Chem. 116, 109–115 (2002)
M.F. Ottaviani, G. Martini, L. Nuti, Magn. Reson. Chem. 25, 897–904 (1987)
G. Audran, P. Brémond, S.R.A. Marque, G. Obame, Chem. Phys. Chem 13(15), 3542–3548 (2012)
S. Jousset, J.-M.P. Catala, Macromolecules 33, 4705–4710 (2000)
F. Le Moigne, A. Mercier, P. Tordo, Tetrahedron Lett. 32(31), 3841–3844 (1991)
F. Gerson, W. Huber, Electron Spin Resonance Spectroscopy of Organic Radicals (Wiley, Weinheim, 2003)
E.G. Bagryanskaya, S.R.A. Marque, Y.P. Tsentalovich, J. Org. Chem. 77(11), 4996–5005 (2012)
P. Stipa, J.-P. Finet, F. Le Moigne, P. Tordo, J. Org. Chem. 58, 4465–4468 (1993)
Acknowledgments
We are grateful to Aix-Marseille University, CNRS and ANR (grant SonRadis ANR-11-JS07-002-0) for their financial support. LB thanks ANR (grant SonRadIs) for a Ph.D. grant. This article was first the topic of a communication at SPIN 2014 in Zelenogradsk, Kaliningrad, Russia.
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Audran, G., Bosco, L., Brémond, P. et al. Solvent Effect in β-Phosphorylated Nitroxides: Model Nitroxides. Appl Magn Reson 46, 1333–1342 (2015). https://doi.org/10.1007/s00723-015-0649-4
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DOI: https://doi.org/10.1007/s00723-015-0649-4