Exposure of a range of alkyl and substituted alkyl iodides in methanol glasses at 77 K to ionizing radiation gave EPR spectra assigned to the alkyl radicals. Irradiation of the pure compounds gave central features assigned to the alkyl radical-iodide ion adducts, together with outer features assigned to the primary σ*-radicals, R∸I.-. These novel results are discussed in terms of the role of the media in governing the species formed. In the case of the I–CH2CO2– and I–CH2OH derivates, species with very large hyperfine coupling to 127I nuclei are thought to be the σ*-radicals I-CH2CO2 ∸ I- and I–CH2O ∸ I-, similar to the I ∸ OMe- radicals previously studied.
References
1.
SpinksJ.W. T, and WoodsR. J., Radiation Chemistry, Wiley-Interscience, New York, 1990.
2.
SpragueE.D., and WilliamsF., J. Chem. Rhys., 1971, 54, 5425.
3.
MishraS.P., and SymonsM. C. R., J. Chem. Soc Perkin Trans.2, 1973, 391.
4.
SymonsM.C. R., J. Chem. Res. (S), 1981, 160; J.B. Raynor, I.J. Rowland and M.C.R. Symons, J. Chem. Soc. Faraday Trans., 1991, 87, 571.
5.
SymonsM.C. R., LindsayD. M., HerschbackD. R., and KwiramA. L., J. Phys. Chem., 1982, 86, 3789; J.B. Raynor, I.J. Rowland and M.C.R. Symons, J. Chem. Soc. Dalton Trans., 1987, 4212.
6.
AsmusD., Acc. Chem. Res., 1979, 12, 436.
7.
SymonsM.C. R., Acta. Chem. Scand., 1997, 51, 127.
8.
NeilsonG.W., SymonsM. C. R., and HuttermanJ., Mol. Phys., 1976, 32, 269.
