Electrochemical synthesis has enabled several sequences of triple chloride bridged diruthenium complexes of general type [L 3− x Cl x RuCl 3RuCl y L 3− y ] z/z+1/z+2 (L = soft neutral ligand) to be generated. The intervalence charge transfer bands in the optical spectra of the mixed-valence Ru II,III 2 compounds and variable temperature magnetic measurements for the corresponding Ru III.III 2 complexes reveal that the degree of metal—metal interaction in these confacial bioctahedral systems decreases as the molecular asymmetry ( y− x) increases.