Compounds of the type M(2)Bz(3) (Bz = benzene, C(6)H(6)) have been of interest since the related triple-decker mesitylenechromium sandwich (1,3,5-Me(3)C(6)H(3))(3)Cr(2) has been synthesized and characterized structurally by X-ray crystallography. Theoretical studies predict the lowest-energy M(2)Bz(3) structures of the early transition metals Ti, V, and Cr to be the triple-decker sandwiches trans-Bz(2)M(2)(eta(6),eta(6)-mu-C(6)H(6)) having quintet, triplet, and singlet spin states, respectively. In these structures, the central benzene ring functions as a hexahapto ligand to each metal atom. The singlet rice-ball cis-Bz(2)M(2)(mu-C(6)H(6)) structures with a 2.64-A Mn=Mn double bond or a 2.81-A Fe-Fe single bond are preferred for the central transition metals Mn and Fe. Singlet triple-decker-sandwich structures trans-Bz(2)M(2)(mu-C(6)H(6)) return as the lowest-energy structures for the late transition metals Co and Ni but with the central benzene ring only partially bonded to each metal atom. Thus, the lowest-energy cobalt derivative has a trans-Bz(2)Co(2)(eta(3),eta(3)-mu-C(6)H(6)) structure in which the central benzene ring acts as a trihapto ligand to each metal atom. Similarly, the lowest-energy nickel derivative has a trans-Bz(2)Ni(2)(eta(2),eta(2)-mu-C(6)H(6)) structure in which the central benzene ring acts as a dihapto ligand to each metal atom, leaving an uncomplexed C=C double bond. The metal metal bond orders in the singlet "rice-ball" structures cis-Bz(2)M(2)(mu-C(6)H(6)) (M = Mn, Fe) and the hapticities of the central benzene rings in the singlet late-transition-metal triple-decker-sandwich structures trans-Bz(2)M(2)(mu-C(6)H(6)) (M = Co, Ni) are governed by the desirability for the metal atoms to attain the favored 18-electron configuration.