Cobalt(II) Dioxygen Carriers Based on Simple Diamino Ligands: Kinetic and ab Initio Studies

The kinetics of the oxygenation reaction of CoL2 2+ complexes (L = ethylenediamine (en), N,Nʹ-dimethylethylenediamnine (dmen)) have been investigated in dimethyl sulfoxide (dmso) at 298 K and in a medium adjused to 0.1 mol dm -3 with Et4NCIO4 by means of a UV-vis spectrophotometric technique. The reaction mechanisms are consistent with the fast formation of superoxo 1:1 initial CoL2-O2 species (L = en, dmen), whereas the dimeric (mu)-peroxo (CoL2)2O2 adduct is formed only when L = en, in the rate determining step. The kinetic results are discussed taking into account the effects of ligand/solvent substitution. EPR results give information on the electronic structure and the coordination geometry of the Co(II) complexes and further confirm the stoichiometry of the species formed. Ab initio calculations provide insights on the geometrical parameters of all the complexes investigated and allow us to draw some hypotheses about the influence of H...H nonbonded interactions in the eventual formation of the dimeric (mu)-peroxo (CoL2)2O2 complexes. Solvational effects are also considered. The formation of the (CoL3)2O2 adduct is also proved when L = en by means of O2 volumetric absorption.