Reactions of Antiaromatic Norcorrole Ni(II) Complex with Carbenes.

Norcorrole is a ring-contracted porphyrinoid, exhibiting distinct antiaromaticity. Herein, we report the reactions of -dimesitylnorcorrole Ni(II) complex with two types of carbenes: dichlorocarbene and an -heterocyclic carbene (NHC). The reaction with in-situ-generated dichlorocarbene resulted in the double insertion of two chloromethine units to provide a mixture of 5,15-dichloroporphyrin and chlorinated isopyricorroles. The nucleophilic NHC attacked the 3-position of the norcorrole core and the subsequent proton transfer furnished a nonconjugated macrocycle incorporating a diazafulvene segment.