Versatile Activity of a Copper(II) Complex Bearing a N ₄ ‐Tetradentate Schiff Base Ligand with Reduced Oxygen Species

The reactivity of the Cu(II) complex N,N’-bis(pyridin-2-ylmethylene)propane-1,3-diamine (py2pn), [Cu(py2pn)(ClO4)2], toward O2.− and H2O2 has been examined. reacts with fast second order kinetics, kMcF=4.05×106 M−1 s−1, employing Cu(II)/Cu(I) couple proved by spectroscopic detection reduced form at low temperature. At −40 °C in DMF, reaction H2O2/Et3N yields an stable end-on Cu(II)-hydroperoxide, kOOH=0.31 min−1, formation which established DFT calculations, electronic EPR spectra. room temperature, Cu(II)-hydroperoxide a to evolve O2, kCAT=83.2 M−2 s−1. can mediate phenol oxidation, probably through trigonal bipyramidal ternary transition state based on analysis, favored over catalase activity when proportion catalyst is used. In these reactions, structural constraints imposed ligand distort coordination geometry metal controls reactivity.