Photochemical generation and reactivity of a new phthalocyanine-manganese-oxo intermediate.

The first phthalocyanine-manganese-oxo intermediate was successfully generated by visible-light photolysis of chlorate or nitrite manganese(III) precursors, and its reactivity towards organic substrates was kinetically probed and compared with other related porphyrin-metal-oxo intermediates.

Visible light generation of high-valent metal-oxo intermediates and mechanistic insights into catalytic oxidations.

High-valent metal-oxo complexes play central roles as active oxygen atom transfer (OAT) agents in many enzymatic and synthetic oxidation catalysis. This review focuses on our recent advances in application of photochemical approaches to probe the oxidizing metal-oxo species with different metals and macrocyclic ligands. Under visible light irradiation, a variety of important metal-oxo species including iron-oxo porphyrins, manganese-oxo porphyrin/corroles, ruthenium-oxo porphyrins, and chromium-oxo salens have been successfully generated.

Formation and kinetic studies of manganese(IV)-oxo porphyrins: Oxygen atom transfer mechanism of sulfide oxidations.

Visible light irradiation of photo-labile porphyrin-manganese(III) chlorates or bromates (2) produced manganese(IV)-oxo porphyrins [Mn(Por)(O)] (Por = porphyrin) (3) in three porphyrin ligands. The same oxo species 3 were also formed by chemical oxidation of the corresponding manganese(III) precursors (1) with iodobenzene diacetate, i.e.