The generation of triplet methoxy cations

The triplet methoxy cation has been generated in the gas phase by the collision induced charge reversal of methoxy anions. Its heat of formation was estimated to be 1034±20 kJ mol−1, in reasonable agreement with ab initio calculations. 3[H3CO]+ and its isomer [H2COH]+ fragment unimolecularly by loss of H2 via a common transition state and some 60% of the reactant's excess energy appears as translational energy of the products. Large isotope effects are involved in the former's fragmentation. The barrier for the isomerization reaction 3[H3CO]+→[H2COH]+ is small, <20 kJ mol−1. The collision induced dissociation 3[H3CO]+→[H3C]++O proceeds via two reaction channels.