Comparative Studies of Structures and Peroxidase-like Activities of Copper(II) and Iron(III) Complexes with an EDTA-Based Phenylene-Macrocycle and Its Acyclic Analogue

Abstract

With the objective of studying the conformational and macrocyclic effects of selected metal chelates on their peroxidase activities, Cu²⁺ and Fe³⁺ complexes were synthesized with a macrocyclic derivative of ethylenediaminetetraacetic acid and o-phenylenediamine (abbreviated as edtaodH₂) and its new open-chain analogue (edtabzH₂). The Fe³⁺ complex of edtaodH₂ has a peroxidase-like activity, whereas the complex of edtabzH₂ does not. The X-ray study of the former shows the formation of a dimeric molecule {[Fe(edtaod)]₂O} in which each metal with an octahedral coordination is overposed over the macrocyclic cavity, as a result of rigid macrocyclic frame, to form an Fe-O-Fe bridge; the exposure of the central metal to the environment facilitates the capture of oxygen to drive the biomimetic activity. The peroxidase-inactive Fe³⁺ complex consists of a mononuclear complex ion [Fe(edtabz)(H₂O)]⁺, the metal ion of which is suited in a distorted pentagonal bipyramid to be protected from environmental oxygen. The copper(II) complexes, which have mononuclear structures with high thermodynamic stability compared with the iron(III) complexes, show no peroxidase activity. The steric effects play a fundamental role in the biomimetic activity.