Paramagnetic H-1 NMR and electron paramagnetic resonance (EPR) spectroscopies and density functional theory (DFT) spin density calculations were selectively performed on the [{(NH3)(5)Ru}(2)(mu-L)](3+') (4+,) (5+) complexes, where L is 2,3,5,6-tetrachloro-, 2,5-dichloro-, 2,5-dimethyl-, and unsubstituted 1,4-dicyanamidobenzene dianion, to characterize the electronic structure of these complexes. EPR spectra of the [{(NH3)(5)Ru}(2)(mu-L)](3+) complexes in N,N'-dimethylformamide at 4 K showed a ruthenium axial signal, and thus the complexes are [Ru(II),L2-, Ru(III)] mixed-valence systems. DFT spin density calculations of [{(NH3)(5)Ru}(2)(mu-L)](3+) where L = 1,4-dicyanamidobenzene dianion gave mostly bridging-ligand centered spin distribution for both vacuum and implicit solvent calculations, in poor agreement with EPR, but more realistic results were obtained when explicit electrostatic interactions between solute and solvent were included in modeling. For the [{(NH3)(5)Ru}(2)(mu-L)](4+) complexes, EPR spectroscopy showed no signal down to 4 K Nevertheless, solvent-dependent H-1 NMR data and analysis support a [Ru(III),L2-, Ru(III)] state. Hyperfine coupling constants (A(c)/h) of trans- and cis-ammine and phenyl hydrogens were determined to be 17.2, 3.8, and -1.5 MHz respectively. EPR studies of the [{(NH3)(5)Ru}(2)(mu-L)](5+) complexes showed a metal-radical axial signal and based on previously published H-1 NMR data, a [Ru(IV),L2-, Ru(III)] state is favored over a [Ru(III),L-, Ru(III)] state.