Abstract
A new tetradentate tetraaza ligand was prepared via Schiff-base condensation of 3,4-diaminotoluene with 2,3-butandione monoxime in aqueous solution. This ligand coordinates cobalt(III) through nitrogen donors in equatorial positions with loss of one oxime proton with concomitant formation of an intramolecular hydrogen bond. A series of cobalt(III) complexes, [CoLX2] (X Cl-, Br-, or I-), [SCNCoLBr], [CNCoLBr], [BF2CoLBr], and [YCoLBr]ClO4 (Y = pyridine, thiophene, triphenylphosphine, or n-pentylamine), was synthesized. The compounds were characterized based on the elemental analysis (C, H, N), electrical conductance, magnetic moment measurements, and spectral studies (IR, H-1 NMR, and UV-Vis). Thermal stabilities of representative complexes were examined by using thermal analysis (TGA and DTG). The reported complexes are d(6) low-spin diamagnetic and a distorted octahedral environment was proposed. All complexes undergo tetragonal distortion as evidenced by splitting of T-1(1g) and T-1(2g) levels of the pseudo-octahedral symmetry. The ligand field parameters such as Dq(E), Dq(A), and the tetragonal splitting D-t have been computed and correlated with the nature of the coordinated axial ligands. The reported cobalt(III) complexes exhibit promising catalytic activity toward aerobic oxidation of ascorbic acid to the corresponding dehydroascorbic acid. The oxidase catalytic activity is linked to both the tetragonal splitting parameter D-t and the Lewis-acidity of cobalt(III) created by the nature of the coordinated axial ligands. The probable mechanistic implications of the catalytic oxidation reactions are discussed.