The oxygen reactivity of catecholatoiron(III) complexes has been examined using a series of catecholate ligands as the substrate. All the complexes examined here, [Fe-III(TPA)(R-Cat)]BPh4 (1-9) (TPA: tris(pyridin-2-ylmethyl)amine; R-Cat: substituted catecholate ligand, R = 3,5-Bu-t(2) (1), 3,6-Bu-t(2) (2), 3,5-Me-2 (3), 3,6-Me-2 (4), 4-Bu-t (5), 4-Me (6), H (7), 4-Cl (8) and 3-Cl (9)), exclusively afforded the intradiol cleaving products of the catecholate ligands upon exposure to O-2. It was revealed that 1-7 can be categorized into two classes based on their electrochemical properties; i.e., the complexes having the dialkyl-substituted (group A) and the mono- or non-substituted (group B) catecholate ligands. In spite of their classification, these two groups show a linear correlation between the logarithm of the reaction rate constant with O-2 and the energy of the catecholate-to-iron(III) LMCT band, although 2 shows a large negative deviation from the correlation line. Based on this LMCT-energy dependent reactivity of 1 and 3-9 as well as the very low reactivity of 2. we have discussed on the mechanisms of the reaction of [Fe-III(TPA)(R-Cat)]BPh4 with O-2. (C) 2004 Elsevier Inc. All rights reserved.