The electronic structures of chromium and vanadium centers coordinated by three reduced 1,2-diketones have been elucidated by using density functional theory (DFT) calculations and a host of physical methods: X-ray crystallography; cyclic voltammetry; ultraviolet-visible (UV-vis), nuclear magnetic resonance (NMR), and electron paramagnetic resonance (EPR) spectroscopy; and magnetic susceptibility measurements. The metal center in octahedral [Cr-III(L-center dot)(3)](0) (1), a Cr-III (d(3)) ion is coupled antiferromagnetically to three monoanionic ligand pi-radicals affording an S = 0 ground state. In contrast, Na-2(Et2O)(2)[V-IV(L-Red)(3)] (2) (S = 1/2), possesses a central V-IV (d(1)) ion 0,0'-coordinated to three closed-shell, doubly reduced ligands which in turn are coordinated by two Na cations enforcing a trigonal prismatic geometry at the vanadium center. 2 can be oxidized electrochemically by one and two electrons generating a monoanion, [V(L)(3)](1-), and a neutral species, [V(L)(3)](0), respectively. DFT calculations at the B3LYP level show that the one-electron oxidized product contains an octahedral V-IV ion coupled antiferromagnetically to one monoanionic ligand pi-radical [V-IV(L-center dot)(L-Red)(2)](1-) (S = 0). In contrast, the two-electron oxidized product contains a V-III ion coupled antiferromagnetically to three ligand pi-radicals in an octahedral field [V-III(L-center dot)(3)](0) (S = 1/2).