Electrochemistry of Oxygenation Catalysts. 3.(1) Thermodynamic Characterization of Electron Transfer and Solvent Exchange Reactions of Co(salen)/[Co(salen)](+) in DMF, Pyridine, and Their Mixtures.

Redox and ligand exchange reactions of the oxygenation catalyst (N,N '-bis(salicylidene)ethylenediaminato)cobalt(II), Co(salen), and its one-electron oxidation product, Co(salen)(+), are investigated in DMF, pyridine, and mixtures of these solvents. Electron transfers and solvent exchange reactions involving three neutral Co(II) and three cationic Co(III) complexes with different axially bound solvent molecules (two DMF, one DMF and one pyridine, or two pyridine molecules) form a three-rung ladder scheme. All formal potentials E(0) and equilibrium constants K in this scheme are determined from electrochemical or spectrophotometric experiments or the construction of thermodynamic cycles.