Unimolecular reactions of isolated organic ions: some isomers of C6H14+˙

Abstract

The slow unimolecular reactions of the four isomers of C₆H₁₄⁺˙ which do not contain a quaternary carbon atom are reported. The results are discussed in terms of a general mechanism involving species comprising a partially formed carbonium ion co-ordinated to an incipient radical. Such species are accessible from the parent C₆H₁₄⁺˙ radicalcation by simply stretching a given C–C bond. In many cases, rearrangement of the partially formed carbonium ion occurs to give thermodynamically more stable isomers. The proposed mechanism also accounts for previously reported energy measurements and ¹³C-labelling data. Further evidence in support of the mechanism is furnished by ²H-labelling experiments.