Reactions of the phenylium cation with small oxygen- and nitrogen-containing molecules

The reactions of phenylium with water and ammonia and their methyl homologs have been investigated using a quadrupole ion trap and semiempirical molecular orbital calculations. The results indicate that both types of molecules react with phenylium through lone pair electrons even though, for methyl-containing compounds, insertion into a C-H bond would lead to more stable products. For the excited adducts formed by reaction with methyl-containing reactant neutrals, the only dissociation observed is loss of a methyl radical. Neutral losses of H2 or CH4, which are more thermodynamically stable, are not observed, which indicates that these reactions are either not kinetically competitive or have high energy transition states due to the fact that the reactions would need to occur via orbital symmetry forbidden 1,2 eliminations.