Ferrioxalate photocatalysis as a versatile system for reductive iron catalysis

A novel photochemical strategy based on the ligand-to-metal charge transfer (LMCT) process of ferrioxalate complexes has been developed. This method represents the first application of ferrioxalate photolysis in synthetic chemistry, enabling the generation of low-valent iron species without the use of strong stoichiometric reductants, while producing carbon dioxide as the sole byproduct. This distinctive activation mode establishes a versatile catalytic platform, base on this platform, a series of novel reductive and cross-coupling transformations have been developed. The platform exhibits broad substrate scope and excellent chemoselectivity, thereby opening new avenues for sustainable iron catalysis.