Reactions of C3H6+ with C3 and C4 Paraffins

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Abstract
Rate constants for H− and H2− transfer from C3 and C4 paraffins to propylene and cyclopropane molecular ions have been determined for ions of low translational energy at the ionization threshold of C3H6+. The results indicate that an increase in KH− is accompanied by a compensating decrease in KH2− and vice versa, such that the total reactivity of C4 structural isomers is invariant. By using selectively labeled compounds, it was possible to derive transfer probabilities for the various substituent sites on the normal butane carbon skeleton. Evidence is also presented which suggests that cyclopropane molecular ions do not assume the propylene‐ion structure prior to or during reaction with C4 paraffins. The results of the present investigation are compared with some complementary data obtained from radiolytic and photolytic systems at much higher pressures.