Manganese Complexes with Consecutive Mn(IV) → Mn(III) Excitation for Versatile Photoredox Catalysis.

Manganese complexes stand out as promising candidates for photocatalyst design, attributed to their eco- and biocompatibility, versatile valence states, and capability for facilitating multiple electronic excitations. However, several intrinsic constraints, such as inadequate visible light response and short excited-state lifetimes, hinder effective photoinduced electron transfer and impede photoredox activation of substrates. To overcome this obstacle, we have developed a class of manganese complexes featuring boron-incorporated N -heterocyclic carbene ligands. These complexes enable prolonged excited-state durations encapsulating both Mn(IV) and Mn(III) oxidation stages, with lifetimes reaching microseconds for Mn(IV) and nanoseconds for Mn(III), concurrently exhibiting robust redox capabilities. They efficiently catalyze direct, site-selective cross-couplings between diverse arenes and aryl bromides, at a low catalyst loading of 0.5 mol %. Their proficiency spans an extensive array of substrates including both highly electron-rich and electron-deficient molecules, which underscore the superior performance of these manganese complexes in tackling intricate transformations. Furthermore, the versatility of these complexes is further highlighted by their successful applications in various photochemical transformations, encompassing reductive cross-couplings for the formation of C-P, C-B, C-S and C-Se bonds, alongside oxidative couplings for creating C-N bonds. This study sheds light on the distinctive photoredox properties and the remarkable catalytic flexibility of manganese complexes, highlighting their immense potential to drive progress in photochemical synthesis and green chemistry applications.