Modulating Effect of Ligand Charge on the Electronic Properties of 2Ni-2S Structures and Implications for Biological 2M-2S Sites.

Sulfur-bridged bimetallic 2M-2S type structures are essential cofactors that participate in biological long-range electron transport and metabolism. Metal-sulfur bond covalency is a decisive property for inner sphere (through-bond) type electron transfer that dominates in buried or hydrophobic protein environments. This work reports on a combined experimental and computational study of the effect of ligand charge on the electronic structure of a 2Ni-2S model site that adopts the biologically relevant