Coordinating properties of acetoxybenziporphyrin, (TPBPOAc)H, have been investigated for a number of metal ions. Insertion of Ni, Pd, and Fe results in the cleavage of the acetoxy group leading to complexes (TPBPO)Ni-II, (TPBPO)Pd-II, and (TPBPO)(FeX)-X-III containing a M-O bond. No cleavage is observed with Zn(II) and Cd(II), which form complexes (TPBPOAc)(MCl)-Cl-II, where M = Zn, Cd. (TPBPO)Ni-II can also be obtained from the dication of hydroxybenziporphyrin, [(TPBPOH)H-3]Cl-2, which is prepared by acid hydrolysis of the acetoxy compound. The diamagnetic (TPBPO)Ni-II can be transformed into the paramagnetic (TPBPOAc)(NiCl)-Cl-II in a reaction with acetyl chloride. X-ray structures have been determined for (TPBPO)Pd-II and (TPBPOAc)(ZnCl)-Cl-II. In the palladium species, the phenolate moiety forms a strong bond to the Pd ion and an unusual interaction geometry is observed, enforced by the macrocyclic environment. Association of a TFA molecule to the phenolic oxygen does not cause significant structural changes in the (TPBPO)Pd-II molecule. In (TPBPOAc)(ZnCl)-Cl-II, the metal ion weakly interacts with the phenolic fragment. The paramagnetic Fe(III) complexes, (TPBPO)(FeX)-X-III, have been investigated with H-1 NMR spectroscopy, The observed spectral patterns are consistent with the presence of a high-spin Fe(III) center and pi delocalization of spin density onto the phenoxide fragment. Each of the compounds (TPBPO)(FeX)-X-III exists in solution as a mixture of two isomers, which for X = 1 are shown to remain in a temperature-dependent equilibrium. The observed isomerism results from two nonequivalent orientations of the axial halide with respect to the puckered macrocyclic ring.