From the Pauson−Khand products 2-ferrocenylcyclopentenone (2) and 2-ferrocenyl-3-methylcyclopentenone (10) as starting materials, substituted ferrocene complexes (C5H5-η5-C5H4)Fe(C5H5) (4), (CH3C5H4-η5-C5H4)Fe(C5H5) (12), and (Me2C5H3-η5-C5H4)Fe(C5H5) (16) were prepared. Metalation of 4, 12, and 16 with Mn(CO)5Br, Cr(CO)3(CH3CN)3, FeCl2(THF) n , and the deprotonated form of [CpFe(fluorene)]+ resulted in good yields of fulvalenyl-bridged heterobi- and polymetallic compounds. The molecular structures of [1-{(C5H4)Fe(C5H5)}-2-CH3C5H4]Mn(CO)3 (13), [2-{(C5H4)Fe(C5H5)}-1,3-Me2C5H2] Mn(CO)3 (17), [2-{(C5H4)Fe(C5H5)}-1,3-Me2C5H2]Fe(C5H5) (18), and [1-{(C5H4)Fe(C5H5)}-2,3,4,5-Me4C5]Fe(C5H5) (23) are reported.