Demetalation of three synthetic zinc cyclic tetrapyrroles that possess identical peripheral substituents, zinc methyl bacteriopyropheophorbide a (zinc bacteriochlorin 1), zinc methyl 3-devinyl-3-acetyl-pyropheophorbide a (zinc chlorin 2), and zinc methyl 3-devinyl-3-acetyl-protopyropheophorbide a (zinc porphyrin 3), was kinetically analyzed under acidic conditions to examine the effects of macrocyclic structures on demetalation without peripheral substitution effects. Zinc bacteriochlorin 1 exhibited much slower demetalation kinetics than zinc chlorin 2 and zinc porphyrin 3. These results indicate that the bacteriochlorin skeleton provides significant resistance to the removal of the central metal from the tetrapyrrole ligand. Comparison of demetalation kinetics of 3-acetyl zinc complexes 2 and 3 with that of 3-vinyl zinc complexes under the same reaction condition demonstrated that the relative ratio (5.0 x 10(-2)) of the demetalation rate constant of the 3-acetyl zinc chlorin 2 to that of the corresponding 3-vinyl zinc chlorin 4 resembled the case of the 3-acetyl zinc porphyrin 3 to the 3-vinyl zinc porphyrin 5 (the relative ratio was 6.8 x 10(-2)). These suggest that the electron-withdrawing 3-acetyl group slows down the demetalation from the tetrapyrrole ligands more than the 3-vinyl group and that the 3-acetyl effect is analogous in both chlorin and porphyrin pi-systems.