Three related diruthenium complexes containing four symmetrical anionic bridging ligands were synthesized and characterized as to their electrochemical and spectroscopic properties. The examined compounds are represented as Ru-2(dpb)(4)Cl, Ru-2(dpb)(4)(CO), and Ru-2(dpb)(4)(NO) in the solid state, where dpb = diphenylbenzamidinate anion. Different forms of Ru-2(dpb)(4)Cl are observed in solution depending on the utilized solvent and the counteranion added to solution. Each Ru-2(5+) form of the compound undergoes multiple redox processes involving the dimetal unit. The reversibility as well as potentials of these diruthenium-centered electrode reactions depends upon the solvent and the bound axial ligand. The Ru-2(5+/4+) and Ru-2(5+/6+) processes of Ru-2(dpb)(4)Cl were monitored by UV-vis spectroscopy in both CH2Cl2 and PhCN. A conversion of Ru-2(dpb)(4)Cl to [Ru-2(dpb)(4)(CO)](+) was also carried out by simply bubbling CO gas through a CH2Cl2 solution of Ru-2(dpb)(4)Cl at room temperature. The chemically generated [Ru-2(dpb)(4)(CO)](+) complex undergoes several electron transfer processes in CH2Cl2 containing 0.1 M TBAClO(4) under a CO atmosphere, and the same reactions were seen for a chemically synthesized sample of Ru-2(dpf)(4)(CO) in CH2Cl2, 0.1 M TBAClO(4) under a N-2 atmosphere, where dpf = N,N'-diphenylformamidinate anion. Ru-2(dpb)(4)(NO) undergoes two successive one-electron reductions and a single one-electron oxidation, all of which involve the diruthenium unit. The CO and NO adducts of Ru-2(dpb)(4) were further characterized by FTIR spectroelectrochemistry, and the IR spectral data of these compounds are discussed in light of results for previously characterized Ru-2(dpf)(4)(CO) and Ru-2(dpf)(4)(NO) derivatives under similar solution conditions.