Presented herein are the first lithium complexes of the porphyrin isomer N-confused porphyrin and its 21-N-methylated variant. In both cases, the macrocycle acts as a monoanionic ligand, and the internal C H bond is retained upon metalation. In the presence the coordinating solvent tetrahydrofuran, pseudo-five-coordinate complexes are generated; in the absence of solvent, the axial positions remain vacant.