A series of first row transition metal complexes with unsupported M-Fe bonds, (3,5-Pr-i(2)-Ar-star)MFe(eta(5)-C5H5)(CO)(2) (M = Fe (1), Mn (2), Cr (3), 3,5-Pr-i(2)-Ar-star = -C6H-2,6-(C6H2-2,4,6-Pr-i(3))(2)-3,5-Pr-i(2)), was synthesized by salt metathesis. They were characterized by H-1 NMR, UV-vis spectroscopy, X-ray crystallography, and SQUID magnetic measurements. Two distinct Fe atoms in 1 were confirmed by Mossbauer spectroscopy. All three compounds feature short metal-metal bond distances (Fe-Fe, 2.3931(8) angstrom (1); Mn-Fe, 2.4512(5) angstrom (2); Cr-Fe, 2.4887(5) angstrom (3)). Their DFT computed structures were in excellent agreement with the experimental data and revealed a dative bonding interaction between the metals.