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Reactions of Antiaromatic Norcorrole Ni(II) Complex with Carbenes
Si-Yu Liu1, Takaki Fukuoka1, Norihito Fukui1
1Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Nagoya 464-8603, Japan.
Abstract:
Norcorrole is a ring-contracted porphyrinoid, exhibiting distinct antiaromaticity. Herein, we report the reactions of meso-dimesitylnorcorrole Ni(II) complex with two types of carbenes: dichlorocarbene and an N-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.
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