meso-Free Corroles: Syntheses, Structures, Properties, and Chemical Reactivities

5,10‐Bis(pentafluorophenyl)corrole (5) and 5,15‐bis(pentafluorophenyl)corrole (9) have been synthesized as meso‐free corroles by rational synthetic routes. Both the structures of these corroles have been unambiguously revealed by X‐ray diffraction analysis and their optical and electrochemical properties have been studied. Chlorination and oxidative dimerization of 5 and 9 have been explored, which revealed a marked different reactivity of the free meso‐positions in 5 and 9. 10‐Chlorinated corrole 11 was effectively prepared by the reaction of 9 with Palau‘chlor in the presence of 1 % pyridine whereas 5‐chlorinated corrole 12 was obtained in a trace amount from similar chlorination of 5. 5,5′‐Linked corrole dimer 13 was produced by reaction of 5 with AgNO2 in a good yield, whereas 10,10′‐linked corrole dimer 14 was formed in a moderate yield by the reaction of 9 with [bis(trifluoroacetoxy)iodo]benzene. Observed large electronic interaction between the two corroles in 13 as compared with that in 14 has been ascribed mainly to conformational flexibility of the former, which allows more coplanar conformation. 5,10 and 5,15‐Diarylcorroles were prepared by acid‐catalyzed condensation reactions followed by 2,3‐dichloro‐5,6‐dicyano‐p‐benzoquinone (DDQ) oxidation (see scheme). The physical properties of these meso‐free corroles have been examined. Chlorination and oxidative dimerization were accomplished, which revealed a marked reactivity difference of the free meso‐positions.