Controlling One-Electron vs Two-Electron Pathways in the Multi-Electron Redox Cycle of Nickel Diethyldithiocarbamate

This manuscript describes electrochemical experiments in which a Nickel(III) intermediate is kinetically trapped by the addition of derivatized pyridine ligands to the electrolyte solution. EPR and DFT studies support the conclusion that pyridine coordinates in a trans- configuration and contains a small equilibrium between mono- and bis-pyridine structures. Electrochemical kinetic data provides evidences for decomposition pathways which ultimately result in Ni(IV) complexes.