Recent studies, particularly from the laboratory of Buchalski and co-workers, have resulted in the syntheses of nickelacyclopentadienyl and nickelafluorenyl metallacycles that can function as pentahapto ligands in transition-metal complexes, similar to the ubiquitous cyclopentadienyl ligand. The structures and energetics of the neutral binuclear chromium carbonyls (CpNiC4H4)(2)Cr-2(CO)n (n = 6, 5, 4, 3; Cp = eta(5)-C5H5) containing the unsubstituted nickelacyclopentadienyl ligand have been investigated by density functional theory. The lowest energy (CpNiC4H4)(2)Cr-2(CO)n (n = 6, 4) structures are similar to the corresponding experimentally characterized Cp2Cr2(CO)n structures with predicted Cr-Cr distances of similar to 3.22 and similar to 2.27 angstrom corresponding to the formal single and triple bonds, respectively. This gives the chromium atoms, as well as the nickel atoms, the favored 18-electron configuration. These species appear to be promising synthetic targets. However, the lowest energy (CpNiC4H4)(2)Cr-2(CO)n (n = 5, 3) structures, as well as two (CpNiC4H4)(2)Cr-2(CO)(4) structures similar to 10 to 12 kcal/mol in energy above the global minimum, can be dissected into a discrete pseudohalogen (CpNiC4H4)Cr(CO)(3) unit and a (CpNiC4H4)Cr(CO)(n-3) unit linked by a Cr-Cr bond flanked by one to three generally weakly semibridging CO groups. In most cases, the chromium atoms in the (CpNiC4H4)Cr(CO)(n-3) units of these structures have 14-16-electron configurations rather than the favored 18-electron configuration. This leads to triplet and even quintet spin states in the lowest energy structures.