Bimolecular reactions of ˙ CH 2 CH 2 OCH: A comparison with the chemical properties of CH 3 CH 2 OCH and ionized trimethylene oxide

The chemical properties of the distonic radical cation ˙ CH 2 CH 2 OCH are compared with those of its conventional isomer, ionized trimethylene oxide, and its even‐electron analog, the ethoxymethyl cation (CH 3 CH 2 OCH ). The rate constants and branching rations have been determined for the gas‐phase reactions of the three ions with several neutral reagents in a dual‐cell Fourier‐transform ion cyclotron resonance device. The reactivity of each ion is found to be quite distinct. Fast electron transfer dominates most of the bimolecular reactions of ionized trimethyleene oxide. The ethoxymethyl cation reacts slowly or not at all with the reagents studied, and the only reaction observed is ethyl cation transfer. The distonic ion ˙ CH 2 CH 2 OCH undergoes vedry fast reactions with all the neutral reagents, and, in sharp contrast to the other two ions, shows remarkably versatile reactivity. This ion rapidly transfers ionized ethylene to most of the neutral molecules studied. Facile electron transfer occurs with some of the neutral reagents while others abstract a pproton from the ion. Abstraction of a radical by the distonic ion‐a reaction reported earlier for dimethyl disulfide—is not observed for any other reagent.