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

Abstract

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–CF3 substituted phosphorus corrole, P–(CF3)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 H2O2 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 H2O2 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.