Among the first representatives of the organometallic bismuth chemistry are a series of iron cyclopentadienyl compounds synthesized by Cullen et al. Characteristic to these is a σ Fe-Bi bond, the iron center bound to 1 cyclopentadienyl and to carbon monoxide ligands only having 17 electron in its coordination sphere in the absence of the Bi bond.
Adding to this, Huttner et al. described the synthesis of mixed Mn-Bi compounds. Most of the synthetic routes use bismuth trichloride as the bismuth metal source. The first proposed route relied on manganese cyclopentadienyl tricarbonyl as the starting material. A better yielding route employed [Cp(CO)Mn(SiPh)] anionic species as the manganese metal source. The synthesized [{Cp(CO)Mn}BiCl] adduct dimerizes in the solid-state.