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The direct conversion of a Mn(III) complex (TBP(8)Cz)Mn(III) (1) to a Mn(V)-oxo complex (TBP(8)Cz)Mn(V)(O) (2) with O(2) and visible light is reported. Complex 1 is also shown to function as an active photocatalyst for the oxidation of PPh(3) to OPPh(3). Mechanistic studies indicate that the photogeneration of 2 does not involve singlet oxygen but rather likely occurs via a free-radical mechanism upon photoactivation of 1.
Prokop et al. (Thu,) studied this question.