Dimeric nickel thiolate complexes have been used to model the structural aspects of the Ni-Fe active site of hydrogenases. Previous studies of monoprotonated and monoalkylated nickel thiolate dimers indicated that alkylation of terminal thiolates caused minimal structural changes, but significant changes in electrochemical behavior, similar to that observed in the Ni-Fe active site of hydrogenase. The current study extends the structural and electrochemical effects upon alkylation to include the dialkylated nickel thiolate dimer. The results of x-ray absorption spectroscopy (XAS), crystallographic, and electrochemical analyses are reported.