Abstract
The reactive scattering of the C7H7+ and C5H5+ products from the collision of Cs+ with o-, m-, and p-chlorotoluenes at 9.5 eV is reported and compared with the results of the similar experiments with α-chlorotoluene. The analogous ’’stripping’’ and ’’rebound’’ mechanisms appear to be operative, with the following principal differences: (1) The C7H7+ ion is probably tropylium in these reactions rather than benzyl; (2) there is a significant inhibitive ’’steric’’ effect due to the neighboring methyl group in the o-chlorotoluene reaction; and (3) the C5H5+ ion from m- and p-chlorotoluenes is produced via an excited tropylium intermediate, while that from o-chlorotoluene seems to come from the decomposition of an excited benzyl ion. The implications for the reaction pathway of the observed ’’propensity rule,’’ that only products with singlet ground states are found at low collision energies, are also discussed.
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