Photocatalytic generation of a non-heme Fe(iii)-hydroperoxo species with O 2 in water for the oxygen atom transfer reaction.

Coupling a photoredox module and a bio-inspired non-heme model to activate O 2 for the oxygen atom transfer (OAT) reaction requires a vigorous investigation to shed light on the multiple competing electron transfer steps, charge accumulation and annihilation processes, and the activation of O 2 at the catalytic unit. We found that the efficient oxidative quenching mechanism between a [Ru(bpy) 3 ] 2+ chromophore and a reversible electron mediator, methyl viologen (MV 2+ ), to form the reducing species methyl viologen radical (MV˙ + ) can convey an electron to O 2 to form the superoxide radical and reset an Fe(iii) species in a catalytic cycle to the Fe(ii) state in an aqueous solution. The formation of the Fe(iii)-hydroperoxo (Fe III -OOH) intermediate can evolve to a highly oxidized iron-oxo species to perform the OAT reaction to an alkene substrate. Such a strategy allows us to bypass the challenging task of charge accumulation at the molecular catalytic unit for the two-electron activation of O 2 . The Fe III -OOH catalytic precursor was trapped and characterized by EPR spectroscopy pertaining to a metal assisted catalysis. Importantly, we found that the substrate itself can act as an electron donor to reset the photooxidized chromophore in the initial state closing the photocatalytic loop and hence excluding the use of a sacrificial electron donor. Laser Flash Photolysis (LFP) studies and spectroscopic monitoring during photocatalysis lend credence to the proposed catalytic cycle.