| Abstract
| - The open-shell benzoylnitrene radical anion, readily generated by electron ionization of benzoylazide,undergoes unique chemical reactivity with radical reagents and Lewis acids in the gas phase. Reactionwith nitric oxide, NO, proceeds by loss of N2 and formation of benzoate ion. This novel reaction is alsoobserved to occur with phenylnitrene anion, forming phenoxide. Similar reactivity was observed in thereaction between benzoylnitrene radical anion and NO2, forming benzoate ion and nitrous oxide. Electronicstructure calculations indicate that the reaction has a high-energy barrier that is overcome by the energyreleased by bond formation. Benzoylnitrene radical anion also transfers oxygen anion to NO and NO2 aswell as to CS2 and SO2. In contrast, phenylnitrene anion reacts with carbon disulfide by C+ or CS+abstraction, forming S- or S2-. Electronic structure calculations indicate that benzoylnitrene in the groundstate resembles a slightly polarized benzoate anion, but with a free radical localized on the nitrogen.
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