Abstract
The structures and reactions of alkane cations (RH +) have been studied by ESR to elucidate the fate of primary cations in radiolysis of alkanes. Radical cations of prototype alkanes such as C 2H 6, C 3H 8, iso-C 4H 10 and neo-C 5H 12 etc. as well as their partially deuterated analogues were stabilized in irradiated frozen matrices such as SF 6, CFCl 2CF 2Cl and CFCl 3 having a higher ionization potential than that of these alkanes contained as dilute solutes. RH + in SF 6 and in CFCl 2CF 2Cl converts into alkyl radicals by deprotonation probably through bimolecular reactions, whereas RH + in CFCl 3 unimolecularily decomposes into olefinic cations by H 2 and/or CH 4 elimination reactions. It is further found that the electronic structures of propane and isobutane cations in halocarbon matrices are different from those in SF 6 and the difference is drastically reflected in the site preference of their deprotonation reactions. The results are discussed in relation to the mechanisms of pairwise formation of alkyl radicals in low temperature radiolysis of neat alkanes and its suppression by addition of electron scavengers.
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