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

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The unique redox cycle of Ni^II(dtc)₂, where dtc^– is N,N-diethyldithiocarbamate, in acetonitrile displays 2e^– redox chemistry upon oxidation from Ni^II(dtc)₂ → [Ni^IV(dtc)₃]⁺ but 1e^– redox chemistry upon reduction from [Ni^IV(dtc)₃]⁺ → Ni^III(dtc)₃ → Ni^II(dtc)₂. The underlying reasons for this cycle lie in the structural changes that occur between four-coordinate Ni^II(dtc)₂ and six-coordinate [Ni^IV(dtc)₃]⁺. Cyclic voltammetry (CV) experiments show that these 1e^– and 2e^– pathways can be controlled by the addition of pyridine-based ligands (L) to the electrolyte solution. Specifically, the addition of these ligands resulted in a 1e^– ligand-coupled electron transfer (LCET) redox wave, which produced a mixture of pyridine-bound Ni(III) complexes, [Ni^III(dtc)₂(L)]⁺, and [Ni^III(dtc)₂(L)₂]⁺. Although the complexes could not be isolated, electron paramagnetic resonance (EPR) measurements using a chemical oxidant in the presence of 4-methoxypyridine confirmed the formation of trans-[Ni^III(dtc)₂(L)₂]⁺. Density functional theory calculations were also used to support the formation of pyridine coordinated Ni(III) complexes through structural optimization and calculation of EPR parameters. The reversibility of the LCET process was found to be dependent on both the basicity of the pyridine ligand and the scan rate of the CV experiment. For strongly basic pyridines (e.g., 4-methoxypyridine) and/or fast scan rates, high reversibility was achieved, allowing [Ni^III(dtc)₂(L)_x]⁺ to be reduced directly back to Ni^II(dtc)₂ + xL. For weakly basic pyridines (e.g., 3-bromopyridine) and/or slow scan rates, [Ni^III(dtc)₂(L)_x]⁺ decayed irreversibly to form [Ni^IV(dtc)₃]⁺. Detailed kinetics studies using CV reveal that [Ni^III(dtc)₂(L)]⁺ and [Ni^III(dtc)₂(L)₂]⁺ decay by parallel pathways due to a small equilibrium between the two species. The rate constants for ligand dissociation ([Ni^III(dtc)₂(L)₂]⁺ → [Ni^III(dtc)₂(L)]⁺ + L) along with decomposition of [Ni^III(dtc)₂(L)]⁺ and [Ni^III(dtc)₂(L)₂]⁺ species were found to increase with the electron-withdrawing character of the pyridine ligand, indicating pyridine dissociation is likely the rate-limiting step for decomposition of these complexes. These studies establish a general trend for kinetically trapping 1e^– intermediates along a 2e^– oxidation path.