Methane activation by alternant [N2O2]+ and [N2S2]+ cluster radical cations

Abstract Methane activation reaction by small alternant [N 2 Y 2 ] + (Y O, S) radical cation rings is predicted by the methods of computational chemistry. Approximate density functional theory and coupled cluster singles and doubles with perturbative triples calculations are employed to investigate the potential energy surface of this putative reaction. On the contrary to previously reported methane activation processes by square planar four-membered rings following the proton coupled electron transfer mechanism, the [N 2 O 2 ] + and [N 2 S 2 ] + clusters, according to our results, may activate methane through the hydrogen atom transfer mechanism. On the contrary, the similar oxide cluster in which the nitrogen atoms were substituted by phosphorous atoms, [P 2 O 2 ] + , does not perform methane activation.