Substituent Effect on the Fe(IV) Corrole Catalyzed Baeyer-Villiger Oxidation Reaction

Comprehending how substituent effect influences catalytic performance is essential for advancing efficient catalysts and unraveling reaction mechanisms. Examining the substituent effects of metal corrole catalyzed Baeyer-Villiger (B-V) oxidation reaction remains limited. In this work, four iron tri-aryl corrole complexes with distinct electronic structures, iron(IV) 5,10,15-tris(pentafluorophenyl) corrole [Fe-IV(TPFC)Cl] (1a), iron(IV) 5,15-bis(pentafluorophenyl)-10-phenyl corrole [Fe-IV(BPFPC)Cl] (2a), iron(IV) 5,15-bis(phenyl)-10-pentafluorophenyl corrole [Fe-IV(BPPFC)Cl] (3a) and iron(IV) 5,10,15-tris(phenyl) corrole [Fe-IV(TPC)Cl] (4a) have been prepared. The impact of electron-withdrawing meso-substituents on their catalytic performance in B-V oxidation reaction was then investigated. The results reveal that an increased number of pentafluorophenyl substituents, which enhance the electron-withdrawing effect, correlates with superior catalytic activity. The catalytic activity follows an order 1a > 2a > 3a > 4a. The plausible mechanism to explain the observed catalytic behavior was also discussed.