Metallocorroles have attracted considerable interest in view of their rich oxidation properties. As the tetrapyrrole 19-membered macrocyclic compound, corrole has the capacity to access higher metal-oxo species, which are more stable than the corresponding porphyrin-metal-oxo species. In this work, a new photochemical method to produce and study high-valent manganese(V)-oxo corrole will be presented. Visible light irradiation of the corresponding highly photo-labile manganese(IV) bromates complexes efficiently generates manganese(V)-oxo intermediates in two different corrole systems, 5,10,15-tris(pentafluorophemyl)corrole (TPFC) and 5,10,15-triphenylcorrole (TPC). The kinetic studies of oxygen transfer atom reactions between organic reductants and manganese(V)-oxo corroles suggest multiple oxidation pathways, where manganese(V)-oxo corroles may serve as direct two-electron oxidant or undergo a disproportionation reaction to form a manganese(VI)-oxo corrole as the true oxidant. The choice of pathways is strongly dependent on the nature of the solvent and the corrole ligand.

Multiple oxidation pathways of photo-generated manganese(V)-oxo corroles

253rd National Meeting (2017)

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