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Hyperfine coupling constants of beta-phosphorylated nitroxides: Subtle interplay between steric strain, hyperconjugation, and dipole-dipole interactions

Abstract : Solvent effects in beta-phosphorylated nitroxides show that nitrogen and phosphorus hyperfine coupling constants a(N) and a(p), increase and decrease with increasing polarity, polarizity, and Hydrogen Bond Donor effects of solvents, respectively. In a series of articles, it was shown that the driving interaction controlling the change in a(p) is the maximization of the N+center dot O-center dot center dot center dot center dot center dot center dot P+-O- dipole - dipole interaction. In this work, we show that the steric strain in Spiro beta-phosphotylated nitroxides affords the opposite trend for a(p) that is, a(p) increases with increasing solvent properties features. (C) 2017 Elsevier Ltd. All rights reserved.
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Submitted on : Monday, April 23, 2018 - 3:00:50 PM
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Paulin Nkolo, Gerard Audran, Paul Bremond, Raphael Bikanga, Sylvain R. A. Marque, et al.. Hyperfine coupling constants of beta-phosphorylated nitroxides: Subtle interplay between steric strain, hyperconjugation, and dipole-dipole interactions. Tetrahedron, Elsevier, 2017, 73 (23), pp.3188--3201. ⟨10.1016/j.tet.2017.04.027⟩. ⟨hal-01774247⟩

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