Reaction of HL, HLa (2-[(2-N-phenylamino)phenylazo]pyridine), HLb (2-[{2-N-(4-methylphenyl)aminolphenylazo]pyridine), or HLc (2-[{2-N-(4-chlorophenyl)aminolphenylazo)pyridine), with KRuO4 or OSO4 and PPh3 under exhaustive deoxygenation (PPh3 -> OPPh3) yields diamagnetic compounds ML2. Crystal structure determination for M(L-a)(2) indicates the radical dianion state, L.2-, for the ligands as evident from the typical N-N bond length of about 1.33 A for a one-electron reduced azo function. The resulting spin-coupled complexes, M-IV(L.2-)(2), can be oxidized in two reversible one-electron steps, as probed by cyclic Voltammetry and UV-vis-NIR spectroelectrochemistry. The paramagnetic intermediates, [M(L-a)(2)](+), are distinguished by intense NIR absorption, largely metal-centered spin as revealed by EPR, and, in the case of [Os(L-a)(2)]I-3, by crystallographically determined shortening of the N = N bond to about 1.30 angstrom, corresponding to a coordinated unreduced azo function. Thus, oxidation of the complex M-IV(L.2-)(2) involves partial reduction of the metal in [M-III(L-)(2)](+) because intramolecular double electron transfer is offsetting the external charge removal. Density-functional theory calculations were employed to confirm the structural features and to support the spectroscopic assignments.