The syntheses and molecular and electronic structures of the following complexes have been established by single crystal X-ray crystallography and UV-vis-NIR spectroscopy, and verified by density functional theory calculations (DFT B3LYP): [(η5-Cp)2ZrIV(tpy2-)]0 ( S = 0) 1, [(η5-Cp)2ZrIV(OMepdi2-)]0 ( S = 0) 2, [CoII(OMepdi•)(η2-BH4)]0 ( S = 0) 4, [RuII(OMepdi-H)Cl(PPh3)2]0 ( S = 0) 5, cis-[RuII(OMepdi0)Cl2(PPh3)]0 ( S = 0) 6, and [RuII(η2-OMepdi0)(η2-OMepdi-H)2]0 ( S = 0) 7, with (tpy0) being neutral 2,2':6',2'́-terpyridine, (tpy•)1- its π radical anion, (tpy2-)2- its dianion; (OMepdi0) neutral 2,6-bis(4-methoxyphenylmethylimine)pyridine, (OMepdi•)1- its radical anion and (OMepdi2-)2- its dianion; (OMepdi-H)1- represents the deprotonated form of the (OMepdi0) ligand where deprotonation takes place at the meta-position of the pyridine ring. Density functional theory calculations using the B3LYP functional were performed, establishing geometry optimized molecular and electronic structures. The structural parameter Δ = [(average distance Cpy-Cimine) - (av. distance Cpy-Npy + av. distance Cimine-Nimime)] is introduced for the characterization of the oxidation level of pdi (and analogously of tpy) ligands of M(pdi) (or M(tpy)) motifs for first row transition metals. The M(L0) unit in second and third row low-valent transition metal ion complexes may exhibit significant π-backdonation M → L0 structural effects.