Role of Solvent Coordination in the Multi-electron Redox Cycle of Nickel Diethyldithiocarbamate.

Nickel(II) diethyldithiocarbamate, NiII(dtc)2, is known to undergo a 2e- ligand-coupled electron transfer (LCET) oxidation to form [NiIV(dtc)3]+. However, the thermodynamics and kinetics of this 2e- process can be greatly affected by solvent coordination. For low coordinating solvents like acetonitrile and acetone, 2e- oxidation is observed via cyclic voltammetry (CV) at a single potential while stronger coordinating solvents like methanol, N,N-dimethylformamide, dimethyl sulfoxide, and pyridine exhibit a 1e- oxidation wave by formation of [NiIII(dtc)2(sol)x]+ intermediates. The decay of these complexes to eventually yield [NiIV(dtc)3]+ was monitored as a function of CV scan rate and temperature to extract rate constants and activation parameters. A thorough analysis of activation parameters revealed that ΔHapp⧧ generally increased with solvent coordination ability, suggesting solvent dissociation was a key factor in the rate limiting step. However, ΔSapp⧧ was found to be negative for all solvents, suggesting an associative mechanism in line with dimer formation with NiII(dtc)2 to facilitate ligand exchange. Density function theory calculations supported the competitive nature of dissociative and associative steps. Using these calculations, we propose two paths for decay of [NiIII(dtc)2(sol)x]+ species based on the coordination strength of the solvent. These studies point to the ability of solvents to either aid or hinder multielectron LCET reactions.