The 1H hyperfine coupling for Me3P˙+ ions generated radiolytically in freon at 77 K (ca. 11.5 G) is much greater than for the dimer cations (Me3P)2+(ca. 3.3 G): this is explained in terms of a decreasign tendency for σ–π delocalisation as the pyramidal character of the Me3P unit increases, coupled with a tendency towards σ-orbital localisation in σ*-radicals.
M. C. R. Symons and G. D. G. McConnachie, J. Chem. Soc., Chem. Commun., 1982, 851 DOI: 10.1039/C39820000851
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