Methylborole iron tricarbonyl, (eta(5)-C4H4BCH3)Fe(CO)(3), is known experimentally and is a potential source of binuclear (C4H4BCH3)(2)Fe-2(CO)(n) (n = 5, 4, 3, 2, 1) derivatives through reactions such as photolysis. In this connection the lowest energy (C4H4BCH3)(2)Fe-2(CO)(5) structures are predicted theoretically to have a single bridging carbonyl group and Fe-Fe distances consistent with formal single bonds. The lowest energy (C4H4BCH3)(2)Fe-2(CO)(4) structures have two bridging carbonyl groups and Fe=Fe distances suggesting formal double bonds. Analogously, the lowest energy (C4H4BCH3)(2)Fe-2(CO)(3) structures have three bridging carbonyl groups and very short Fe Fe distances suggesting formal triple bonds. The tetracarbonyl (C4H4BCH3)(2)Fe-2(CO)(4) is predicted to be thermodynamically unstable toward disproportionation into (C4H4BCH3)(2)Fe-2(CO)(5) + (C4H4BCH3)(2)Fe-2(CO)(3), whereas the tricarbonyl is thermodynamically viable toward analogous disproportionation. The lowest energy structures of the more highly unsaturated methylborole iron carbonyls (C4H4BCH3)(2)Fe-2(CO)(n) (n = 2, 1) have hydrogen atoms bridging an iron-carbon bond. In addition, the lowest energy (C4H4BCH3)(2)Fe-2(CO) structures are "slipped perpendicular" structures with bridging methylborole ligands, a terminal carbonyl group, and agostic CH3 -> Fe interactions involving the methyl hydrogens. Thus, in these highly unsaturated systems the methyl substituent in the methylborole ligand chosen in this work is not an "innocent bystander" but instead participates in the metal-ligand bonding.