A density functional theoretical (DFT) study (B3LYP) has been carried out on 20 organometallic complexes containing eta(5)- and/or eta(3)-coordinated cyclopentadienyl anions (Cp-) and 2,2 '-bipyridine (bpy) ligand(s) at varying oxidation levels, i.e., as the neutral ligand (bpy(0)), as the pi-radical monoanion (bpy(center dot-))(-), or as the diamagnetic dianion (bpy(2-))(2-). The molecular and electronic structures of these species in their ground states and, in some cases, their first excited states have been calculated using broken-symmetry methodology. The results are compared with experimental structural and spectroscopic data (where available) in order to validate the DFT computational approach. The following electron-transfer series and complexes have been studied: [(Cp)(2)V(bpy)](0,+,2+) (1-3), [(Cp)(2)Ti(bpy)](-,0,+,2+) (4-7), [(Cp)(2)Ti(biquinoline)](0,+) (8 and 9), [(Cp*)(2)Ti(bpy)](0) (10) (Cp* = pentamethylcyclopentadienyl anion), [Cp*Co(bpy)](0,+) (11 and 12), [Cp*Co(bpy)Cl](+,0) (13 and 14), [Fe(toluene)(bpy)](0) (15), [Cp*Ru(bpy)](-) (16), [(Cp)(2)Zr(bpy)](0) (17), and [Mn(CO)(3)(bpy)](-) (18). In order to test the predictive power of our computations, we have also calculated the molecular and electronic structures of two complexes, A and B, namely, the diamagnetic dimer [Cp*Sc(bpy)(mu-Cl)](2), (A) and the paramagnetic (at 25 degrees C) mononuclear species [(eta(5)-C5H4(CH2)(2)N(CH3)(2))Sc((m)bpy)(2)] (B). The crystallographically observed intramolecular pi-pi interaction of two N,N'-coordinated pi-radical anions in A leading to an S = 0 ground state is reliably reproduced. Similarly, the small singlet-triplet gap of similar to 600 cm(-1) between two antiferromagnetically coupled (bpy(center dot-))(-) ligands in B, two ferromagnetically coupled radical anions in the triplet excited state of B, and the structures of A and B is reproduced. Therefore, we are confident that we can present computationally obtained, detailed electronic structures for comlexes 1-18. We show that N,N'-coordinated neutral bpy ligands behave as very weak pi acceptors (if at all), whereas the (bpy(2-))(2-) dianions are strong pi-donor ligands.