An iron-rhodium bimetallic complex bearing a six-membered metallacycle was synthesized from a lithium bis(iminophosphorane)iron complex, which served as an anionic chelating ligand carrying a bis(iminophosphorano)methanide-like inorganic framework. The metallacycle complex takes a peculiar boat shape, in which the two metal centers are in close proximity and the carbonyl ligand on the iron atom overhangs the rhodium atom, giving a considerably low-frequency IR absorption and assuming a slightly bent structure.