Terminal cobalt(IV)–oxo (Co^IV–O) species have been implicated as key intermediates in various cobalt-mediated oxidation reactions. Herein we report the photocatalytic generation of a mononuclear non-haem [(13-TMC)Co^IV(O)]²⁺ (2) by irradiating [Co^II(13-TMC)(CF₃SO₃)]⁺ (1) in the presence of [Ru^II(bpy)₃]²⁺, Na₂S₂O₈, and water as an oxygen source. The intermediate 2 was also obtained by reacting 1 with an artificial oxidant (that is, iodosylbenzene) and characterized by various spectroscopic techniques. In particular, the resonance Raman spectrum of 2 reveals a diatomic Co–O vibration band at 770 cm⁻¹, which provides the conclusive evidence for the presence of a terminal Co–O bond. In reactivity studies, 2 was shown to be a competent oxidant in an intermetal oxygen atom transfer, C–H bond activation and olefin epoxidation reactions. The present results lend strong credence to the intermediacy of Co^IV–O species in cobalt-catalysed oxidation of organic substrates as well as in the catalytic oxidation of water that evolves molecular oxygen.

The detailed mechanism of CO ₂ reduction by a cobalt( i ) complex is investigated using computations and kinetics.