Platinum(II) and palladium(II) complexes [M(CH₃)(L)]SbF₆ with substituted terpyridine ligands L undergo light-driven oxygen insertion reactions into metal methyl bonds resulting in methylperoxo complexes [M(OOCH₃)(L)]SbF₆. The oxygen insertion reactions occur readily for complexes with methyl ligands that are activated due to steric interaction with substituents (NH₂, NHMe or CH₃) at the 6,6″-positions on the terpyridine ligand. All complexes exhibit attractive intermolecular π···π or M···M interactions in the solid state and in solution, which lead to excited triplet dinuclear M–M complexes upon irradiation. A mechanism is proposed whereby a dinuclear intermediate is generated upon irradiation that has a weakened M–C bond in the excited state, resulting in the observed oxygen insertion reactions.