The high-valent bis(oxo)-bridged dimanganese(IV) complexes with the series of binucleating 4.5-X-2-o-phenylenebis(oxamate) ligands (opbaX(2); X = H, Cl, Me) (1a-c) have been synthesized and characterized structurally, spectroscopically and magnetically. Complexes la-c possess unique Mn-2(mu-O)(2) core structures with two o-phenylenediamidate type additional bridges which lead to exceptionally short Mn-Mn distances (2.63-2.65 angstrom) and fairly bent Mn-O-Mn angles (94.1 degrees-94.6 degrees). The cyclovoltammograms of la-c in acetonitrile (25 degrees C, 0.1 M Bu4NPF6) show an irreversible one-electron oxidation peak at moderately high anodic potentials (E-ap = 0.50-0.85 V versus SCE), while no reductions are observed in the potential range studied (down to -2.0 V versus SCE). These dinuclear manganese oxamate complexes are excellent catalysts for the aerobic oxidation of 3,5-di-tert-butylcatechol to the corresponding o-quinone in acetonitrile at 25 degrees C. The order of increasing catecholase activity (k(obs)) with the electron donor character of the ligand substituents as 1b (X = Cl) < 1a (X = H) < 1c (X = Me) correlates with Hammett sigma(+) values (p = -0.95). A mechanism involving initial activation of the catechol substrate by coordination to the dimetal center and subsequent oxidation to quinone by O-2 is proposed, which is consistent with the observed saturation kinetics. (c) 2006 Elsevier B.V. All rights reserved.