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

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Abstract

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.

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Notes

  1. As far as we know, this nitroxide has only been observed through spin-trapping experiments involving the addition of 2-diethoxyphoshorylprop-2-yl radical onto tert-butyl nitroso. Consequently, its preparation on a large scale by a conventional procedure is not so obvious.

  2. θ the dihedral angle between the C–P bond and the Singly Occupied Molecular Orbital SOMO (Fig. 2) on the nitrogen atom of the nitroxyl moiety. ρ πN , the electron density on the nitrogen atom of the nitroxyl moiety, is proportional to a N. B 0 is the transfer of the spin density through the spin polarization process and B 1 is the transfer of the spin density through the hyperconjugation process. In general, B 0 is very small and can be neglected. See Ref. [9]. Values of B 1 are dependent on the atom or on the group at position β See Refs. [9, 17].

  3. CCDC: 1450111. The related X-ray parameters are provided in SI.

  4. This conformation is the most stable as only one strong methyl-methyl 1,3-syn interaction is observed instead of 3 strong interactions in the conformer with t-BuMe2SiO and (EtO)2(O)P in axial positions (Me-t-BuMe2SiO, Me-(EtO)2(O)P and, t-BuMe2SiO-(EtO)2(O)P, not shown).

  5. Many other parameters available in the literature can be used to describe the different terms of Eq. (18). Here, only the parameters used for the KP and KAT correlations are discussed.

  6. As quoted by Reichardt (Ref. [12]): “A cybotactic region may be defined as the volume around a solute molecule in which the ordering of the solvent molecules has been influenced by the solute, including both the first solvation shell and the transition region”.

  7. At the first glance, geometrical requirements for H-bonding are expected to be fulfilled for all nitroxides.

References

  1. G. Likhtenshtein, J. Yamauchi, S. Nakatsuji, A.I. Smirnov, R. Tamura, Nitroxides: Applications in Chemistry, Biomedicine, and Materials Science (Wiley-VCH, Weinheim, 2008)

    Book  Google Scholar 

  2. R. Hicks (ed.), Stable Radicals: Fundamentals and Applied Aspects of Odd-Electron Compounds (Wiley, Hoboken, N.J., 2010)

    Google Scholar 

  3. A. Kirilyuk, A.A. Bobko, V.V. Khramtsov, I.A. Grigor’ev, Org. Biomol. Chem. 3, 1269–1274 (2005)

    Article  Google Scholar 

  4. V. Belle, S. Rouger, S. Costanzo, S. Longhi, A. Fournel, in Instrumental Analysis of Intrinsically Disordered Proteins: Assessing Structures and Conformations, ed. by V.N. Uversky, S. Longhi (Wiley, Hoboken, N.J., 2010), pp. 131–169

  5. P. Mellet, P. Massot, G. Madelin, S.R.A. Marque, E. Harte, J.-M. Franconi, E. Thiaudière, PLoS One. 4, e5244 (2009)

    Article  ADS  Google Scholar 

  6. H. Karoui, F. Le Moigne, O. Ouari, P. Tordo, in Stable Radicals: Fundamentals and Applied Aspects of Odd-Electron Compounds, ed. by R. Hicks (Wiley, Hoboken, N.J., 2010), pp. 173–229

  7. V. Ovcharenko, in Stable Radicals: Fundamentals and Applied Aspects of Odd-Electron Compounds, ed. by R. Hicks (Wiley, Hoboken, N.J., 2010), pp. 461–506

  8. B.R. Knauer, J.J. Napier, J. Am. Chem. Soc. 98, 4395 (1976)

    Article  Google Scholar 

  9. E.G. Janzen, G.A. Coulter, U.M. Oehler, J.P. Bergsma, Can. J. Chem. 60, 2725 (1982)

    Article  Google Scholar 

  10. C.H. Deng, C.J. Guan, M.H. Shen, C.X. Zhao, J. Fluorine Chem. 116, 109 (2002)

    Article  Google Scholar 

  11. A.Sh. Mukhtarov, A.V. Il’yasov, Ya.A. Levin, I.P. Gozman, M.S. Skorobogatova, E.I. Zoroatskaya, Theor. Exp. Chem. 12, 656 (1976); Teor. Eksp. Khim. 12, 831 (1976)

    Article  Google Scholar 

  12. C. Reichardt, T. Welton, Solvent and Solvent Effect in Organic Chemistry, 4th ed. (Wiley-VCH, Weinheim, 2011)

  13. G. Audran, L. Bosco, P. Brémond, J.-M. Franconi, N. Koonjoo, S.R.A. Marque, P. Massot, P. Mellet, E. Parzy, E. Thiaudière, Angew. Chem. Int. Ed., 54(45), 13379 (2015)

    Article  Google Scholar 

  14. G. Audran, L. Bosco, P. Brémond, T. Butscher, S.R.A. Marque, Org. Biomol. Chem. 14, 1228 (2016)

    Google Scholar 

  15. G. Audran, L. Bosco, P. Brémond, T. Butscher, S.R.A. Marque, Appl. Magn. Reson., 45(12), 1333 (2015)

    Article  Google Scholar 

  16. G. Audran, L. Bosco, P. Brémond, T. Butscher, J.-M. Franconi, K. Kabitaev, S.R.A. Marque, P. Mellet, E. Parzy, M. Santelli, E. Thiaudière, S. Viel, RSC Adv., 6, 5653–5670 (2016)

    Article  Google Scholar 

  17. F. Gerson, W. Huber, Electron Spin Resonance Spectroscopy of Organic Radicals (Wiley-VCH, Weinheim, 2003)

    Book  Google Scholar 

  18. S. Marque, J. Org. Chem. 68, 7582 (2003)

    Article  Google Scholar 

  19. E.G. Bagryanskaya, S.R.A. Marque, Y.P. Tsentalovich, J. Org. Chem. 77, 4996 (2012)

    Article  Google Scholar 

  20. E.G. Bagryanskaya. S.R.A. Marque, Chem. Rev. 114, 5011 (2014)

    Article  Google Scholar 

  21. M. Charton, Prog. Phys. Org. Chem. 13, 119 (1981)

    Article  Google Scholar 

  22. H. Fischer, A. Kramer, S.R.A. Marque, P. Nesvadba, Macromolecules 38, 9974 (2005)

    Article  ADS  Google Scholar 

  23. G. Audran, P. Brémond, S.R.A. Marque, G. Obame, ChemPhysChem 13, 3542 (2012)

    Article  Google Scholar 

  24. P. Stipa, J.-P. Finet, F. Le Moigne, P. Tordo, J. Org. Chem. 58, 4465 (1993)

    Article  Google Scholar 

  25. Y. Marcus, The Properties of Solvents Vol. 4, (Wiley, Chichester, 1998)

    Google Scholar 

  26. G. E. Zaikov, R. G. Makitra, G. G. Midyana, L. I. Bazylyak, Influence of the Solvent on Some Radical Reaction, Chemistry Research and Applications Series (Nova Science Publishers Inc., New York, 2010)

    Google Scholar 

  27. J. Shorter, Correlation Analysis of Organic Reactivity (J. Wiley & Sons, New York, 1982), pp. 73–126

    Google Scholar 

  28. J. Shorter, Correlation Analysis of Organic Reactivity (J. Wiley & Sons, New York, 1982), pp. 9–25

    Google Scholar 

  29. A. Debuigne, D. Chan-Seng, L. Li, G.K. Hamer, M.K. Georges, Macromolecules 40, 6224 (2007)

    Article  ADS  Google Scholar 

  30. R. Katritzky, M. Kuanar, S. Slavov, C.D. Hall, M. Karelson, I. Kahn, D.A. Dobchev, Chem. Rev. 110, 5714 (2010)

    Article  Google Scholar 

  31. A. Koppel, V.A. Palm, in Advances in Linear Free Energy Relationships chapter 5, ed. by N.B. Chapman, J. Shorter (Plenum Press, London, New York, 1972), p. 203

    Chapter  Google Scholar 

  32. G.A. Jeffrey, W. Saenger, Hydrogen Bonding in Biological Structures (Springer-Verlag, Berlin, Heidelberg, 1994)

    Google Scholar 

  33. R.S. Rowland, R. Taylor, J. Phys. Chem. 100, 7384 (1996)

    Article  Google Scholar 

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Acknowledgements

We thank Aix-Marseille University, CNRS for financial support and Prof. Audran for advice in synthesis. SRAM thanks the Russian Science Foundation (project no. 15-13-20020) for supporting the correlation analysis. We thank RENARD network for the EPR platform.

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Authors and Affiliations

  1. Aix-Marseille Université, CNRS-UMR 7273, ICR, Case 551, Avenue Escadrille Normandie-Niemen, 13397, Marseille Cedex 20, France

    Lionel Bosco, Teddy Butscher & Sylvain R. A. Marque

  2. N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, Pr. Lavrentjeva 9, 630090, Novosibirsk, Russia

    Sylvain R. A. Marque

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  1. Lionel Bosco
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Correspondence to Sylvain R. A. Marque.

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Bosco, L., Butscher, T. & Marque, S.R.A. β-Phosphorus Hyperfine Coupling Constant in Nitroxides: Conformational Effects in 6-Membered Ring Nitroxides. Appl Magn Reson 48, 379–406 (2017). https://doi.org/10.1007/s00723-017-0867-z

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