Potential energy profiles for the unimolecular reactions of organic ions: some isomers of C3H8N+ and C4H10N+

Abstract

The slow, unimolecular reactions of the isomeric ions C₃H₈N⁺ which contain the NH₂ group are discussed in terms of a potential energy profile approach, in conjunction with the organic chemist's concept of mechanism. The approach successfully explains the slow reactions undergone by these ions and also rationalises the results of previous deuterium labelling studies. Extension of the approach to the three isomers of C₄H₁₀N⁺ which also contain the NH₂ group results in various predictions concerning the reactions undergone by these ions. It is found that the observed behaviour is in excellent agreement with that expected both in the extent of the reactions undergone and also the shapes of the metastable peaks for the processes concerned.