Abstract
A method for the study of reactions of open-shell neutrals (radicals) and radical cations is described. Pyrolysis (25–1500 °C) of thermally labile compounds, such as, 1,5-hexadiene via a Chen nozzle yields a seeded beam of reactive species in helium. The pyrolysis products are then analyzed by electron ionization (EI) or reacted with stored ions. Electron ionization of the pyrolysis products of 1,5-hexadiene shows that both the allyl radical and allene are generated. Reactions of benzene radical cations and the pyrolysis products of 1,5-hexadiene result in carbon–carbon bond formation. Those reactions of allyl radical with the benzene radical cation yield the C 7H 7 + ion of m/ z 91, permitting an unusual entry into arenium ions. The reaction of allene with benzene radical cation in contrast yields C 9H 10 + and C 9H 9 +.
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