A lignin-derived ligand, bis(2-hydroxy-3-methoxy-5-propylbenzypglycine (DHEG), was synthesized from 2-methoxy-4-propylphenol (dihydroeugenol (DHE)) and the amino acid glycine. Two mononuclear iron and manganese complexes of DHEG were prepared, characterized, and employed for the oxidation of chlorite to chlorine dioxide in aqueous solution. Peroxyacetic acid (PAA) was used as a "green" oxidant in the redox reactions to initiate the formation of high-valent Fe and Mn (IV)-OH intermediates. EPR studies verified the formation of a high-valent Mn-IV species. Both Fe and Mn complexes catalyzed chlorite oxidation with bimolecular rate constants of 32 and 144 M-1 s(-1), respectively, at pH 4.0 and 25 degrees C. The Mn complex was found to be more efficient for chlorite oxidation with a turnover frequency of 17 h(-1) and remained active during subsequent additions of PAA. The rate of ClO2 decomposition with PAA/Mn-DHEG was first order in PAA and increased significantly as pH increased. A mechanism that accounts for all observations is presented.