The diamagnetic compounds Cp'2Ni2E2 (1: E = S, 2: E = Se, 3: E = Te; Cp' = 1,2,3,4,-tetraisopropylcyclopentadienyl), first reported by Sitzmann and co-workers in 2001 [Sitzmann, H.; Saurenz, D.; Wolmershauser, G.; Klein, A.; Boese, R. Organometallics 2001, 20, 700], have unusual E center dot center dot center dot E distances, leading to ambiguities in how to best describe their electronic structure. Three limiting possibilities are considered: case A, in which the compounds contain singly bonded E-2(2)- units; case B, in which a three-electron E-E half-bond exists in a formal E-2(3-) unit; case C, in which two E-2(-) ions exist with no formal E-E bond. One-electron reduction of 1 and 2 yields the new compounds [Cp*Co-2][Cp'2Ni2E2] (1red: E = S, 2red: E = Se; Cp* = 1,2,3,4,5-pentamethylcyclopentadieyl). Evidence from X-ray crystallography, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy suggest that reduction of 1 and 2 is Ni-centered. Density functional theory (DFT) and ab initio multireference methods (CASSCF) have been used to investigate the electronic structures of 1-3 and indicate covalent bonding of an E23- ligand with a mixed-valent Ni-2(II,III) species. Thus, reduction of 1 and 2 yields Ni2(II,II) species 1red and 2red that bear unchanged E-2(3-) ligands. We provide strong computational and experimental evidence, including results from a large survey of data from the Cambridge Structural Database, indicating that M2E2 compounds occur in quantized E-2 oxidation states of (2 x E2-), E-2(3-), and E-2(2-), rather than displaying a continuum of variable E-E bonding interactions.