A series of diruthenium compounds, Ru-2(DArF)(3)(L")Cl (2), where the auxiliary ligand DArF is DmAniF or D(3,5-Cl2Ph)F and L" is one of the diarylformamidinate ligands containing at least one biphenyl, were prepared from Suzuki reactions between Ru-2(DArF)(3)(L') Cl (1), where L' is (4-I-Ph)NC(H)NPh (N-(4-iodophenyl)-N'-phenylformamidinate) or D(4-I-Ph)F (N,N'-di(4-iodophenyl)formamidinate), and ArB(OH)(2) (Ar = Ph and 4-CH3C(O)Ph) in satisfactory yields. Alkynylation of the type 2 compounds with LiCCPh yielded the alkynyl derivatives Ru-2(DArF)(3)-(L")(CCPh) (3). Alternatively, type 3 compounds can be prepared from the Suzuki coupling reaction between Ru-2(DArF)(3)(L')(C2Ph) and ArB(OH)(2). A structural comparison between the type 1 and 2 compounds revealed minimal changes in the coordination sphere of Ru-2 core. Cyclic voltammograms of Suzuki derivatives resemble those of the parent compounds, indicating the retention of the electrophore characteristic of diruthenium species upon peripheral modification.