Organic radical ions unimolecular reactions

New synthetic transformations are highly dependent on the dynamics of the contact ion pair, as well as reactivity of the individual radical ions. For example, the electron-transfer paradigm is most efficient with those organic donors yielding highly unstable cation radicals that undergo rapid unimolecular reactions. Thus, the hexamethyl(Dewar)benzene cation radical that is generated either via CT activation of the [D, A] complex with tropylium cation,74... 

Such unimolecular ion-decomposition reactions can be viewed as another field of chemistry, but fortunately for most chemists studying this book, there are many close similarities to pyrolytic, photolytic, radiolytic, and other energetic reactions, and there are even many general similarities to condensed-phase (solution) organic reactions. The largest points of difference are that ionic and often radical species are involved in each reaction in the mass spectrometer, and their combined effects sometimes appear unusual to the organic chemist. Chemists may also question the reliability of structural relationships based on rearrangement reactions. However, many of these are based on well-established chemistry and can provide key molecular information... 

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