Azulene is reported to react with Mn(2)(CO)(10) to give trans-C(10)H(8)Mn(2)(CO)(6), which has been shown by X-ray crystallography to have a bis(pentahapto) structure with no metal-metal bond. This structure is found by density functional theory to be the lowest energy C(10)H(8)Mn(2)(CO)(6) structure. However, a corresponding bis(pentahapto) cis-C(10)H(8)Mn(2)(CO)(6) structure, also without an Mn···Mn bond, lies within ~1 kcal mol(-1) of this global minimum. The lowest energy C(10)H(8)Mn(2)(CO)(5) structure is singlet cis-η(5),η(5)-C(10)H(8)Mn(2)(CO)(5) with an Mn→Mn dative bond from the Mn(CO)(3) group to the Mn(CO)(2) group. However, a singlet cis-η(6),η(4)-C(10)H(8)Mn(2)(CO)(5) structure with a normal Mn-Mn single bond lies within ~6 kcal mol(-1) of this global minimum. The lowest energy structures of the more highly unsaturated C(10)H(8)Mn(2)(CO)(n) (n = 4, 3, 2) systems all have cis geometries and manganese-manganese bonds of various orders. The corresponding global minima are triplet cis-η(5),η(3)-C(10)H(8)Mn(2)(CO)(3)(η(2)-μ-CO) for the tetracarbonyl with a four-electron donor bridging carbonyl group, singlet cis-η(5),η(5)-C(10)H(8)Mn(2)(CO)(3) for the tricarbonyl, and triplet cis-η(6),η(4)-C(10)H(8)Mn(2)(CO)(η(2)-μ-CO) for the dicarbonyl.