Concepts of metal-mediated methane functionalization.: An intersection of experiment and theory

Concepts for the activation of methane are derived from ion-molecule reactions of mass-selected, ground-state transition-metal cations M+. Elementary steps of industrially important processes are uncovered (e.g., oxygenation of methane or its coupling with carbon dioxide). In addition, the implications of the electronic structures of M(CH2)(+) complexes for their reactions with nucleophiles are discussed, and the crucial role of contemporary quantum mechanical calculations in the elucidation of mechanistic details is emphasized.