Extended metal atom chains constitute an interesting class of molecules from both theoretical and applied points of view. In the chromium-based series Cr 2 M(dpa) 4 X 2 (with M = Zn, Ni, Fe, Mn, Cr), the direct metal−metal interactions span a wide range of possibilities and so do their associated properties. The multiplicity and symmetry components of the metal−metal bond are herein analyzed via the effective bond order (EBO) concept using complete active space self-consistent field wave functions and compared with similar bimetallic Cr 2 L 4 X 2 systems. The bond multiplicity follows a trend dominated by the Cr−Cr distance which, in turn, depends on the nature of the axial ligand (X). Cr 2 M compounds present asymmetric structures with virtually no interaction between the Cr 2 unit and M, whereas fully symmetric structures with delocalized bonding among the three metals are also possible in Cr 3 complexes. In such cases, a strategy that involves localization of the molecular orbitals into each Cr−Cr pair is applied to quantify the contribution of each pair to the overall metal−metal bond multiplicity.