Synthesis, characterization and antioxidant activity of water soluble MnIII complexes of sulphonato-substituted Schiff base ligands

Two new Mn-III complexes Na[Mn(5-SO3-salpnOH)(H2O)] center dot 5H(2)O (1) and Na[Mn(5-SO3-salpn)(MeOH)]center dot 4H(2)O (2) (5-SO3-salpnOH = 1,3-bis(5-sulphonatosalicylidenamino)propan-2-ol, 5-SO3-salpn = 1,3-bis(5-sulphonatosalicylidenamino)propane) have been prepared and characterized. Electrospray ionization-mass spectrometry, UV-visible and H-1 NMR spectroscopic studies showed that the two complexes exist in solution as monoanions [Mn(5-SO3-salpn(OH))(solvent)(2)](-), with the ligand bound to Mn-III through the two phenolato-O and two imino-N atoms located in the equatorial plane. The E-1/2 of the Mn-III/Mn-II couple (-47.11 (1) and -77.80 mV (2) vs. Ag/AgCl) allows these complexes to efficiently catalyze the dismutation of O-2(center dot), with catalytic rate constants 2.4 x 10(6) (1) and 3.6 x 10(6) (2) M-1 s(-1), and IC50 values of 1.14(1) and 0.77 (2) mu M, obtained through the nitro blue tetrazolium photoreduction inhibition superoxide dismutase assay, in aqueous solution of pH 7.8. The two complexes are also able to disproportionate up to 250 equivalents of H2O2 in aqueous solution of pH 8.0, with initial turnover rates of 178 (1) and 25.2 (2) mM H2O2 min(-1) mM(-1) catalyst(-1). Their dual superoxide dismutase/catalase activity renders these compounds particularly attractive as catalytic antioxidants. (C) 2009 Elsevier Inc. All rights reserved.