Corrole–chelated phosphorus complex: enabling dual C–H chlorination and H₂O₂ generation

We are presenting a groundbreaking study on the use of a main group phosphorus corrole complex, P–(CF 3 ) 5 , as an efficient photocatalyst for chlorination reactions. Through the optimizations of catalyst selection, solvent choice and acid concentration, we achieved remarkable catalytic efficiencies. Meanwhile, this innovative system simultaneously generates H₂O₂, with its production optimized for maximum efficiency. Supported by DFT calculations, our study elucidates a reactive oxygen species–triggered mechanism, demonstrating the potential of non–precious main group systems as viable photocatalysts. This work opens new avenues for applying sustainable, eco–friendly photocatalysts in essential industrial organic processes, marking a significant advancement in green chemistry. • Efficient photocatalytic chlorination of aromatics was achieved using P–corrole. • Dual catalysis was observed in both chlorination and H 2 O 2 formation. • Reproducibility and stability over multiple cycles highlight its practical utility. Corroles, despite their highly tunable and excellent photophysical and electrochemical properties, have rarely been explored as mainstream photocatalytic photosensitizers. Our study introduces a novel application of the highly oxidizing penta–CF 3 substituted phosphorus corrole, P–(CF 3 ) 5 , which has shown remarkable efficacy in the chlorination of phenol and related natural compounds (the beta 2, 3, 8, 17, 18-substituted isomer: 2,3,8,17,18–pentatrifluoromethyl–(5,10,15–tris(pentafluorophenyl) corrole phosphorus (V) difluoride). Here, we report the first case of the simultaneous photocatalytic chlorination of phenol or toluene and H 2 O 2 formation, with the latter achieving a notable rate of > 7 mM/g/h under ambient conditions. Notably, the oxidation of toluene predominantly yields benzaldehyde over benzyl chloride. The H 2 O 2 formation can be finely tuned by adjusting the water/acetonitrile ratio and acid concentration. Comprehensive experimental and theoretical (DFT) investigations were conducted to elucidate the underlying mechanisms of both chlorination and oxidation. This dual–function catalytic process not only enhances reaction efficiency but also underscores the potential of corrole–based catalysts in advancing sustainable and green chemical methodologies.