The metallation of the eta(5)-C5H5(CO)(2)Fe-eta(1),eta(5)-C5H4Mn(CO)(3) and complex with (BuLi)-Li-n (THF, -78 degrees C) followed by the treatment of the lithium derivative with Ph2PCl afforded the eta(5)-Ph2PC5H4(CO)(2)Fe-eta(1),eta(5)-C5H4Mn(CO)(3) complex. The reaction of the latter with eta(5)-C5H5(CO)(2) WCl in the presence of Me 3 NO produced the trinuclear complex eta(5)-C5H5(CO)(2) W-eta(5)-(Ph2P)C5H5(CO)(2)Fe-eta(1),eta(5)-C5H4Mn(CO)(3). The structure of the latter complex was established by IR, UV, and H-1 and P-31 NMR spectroscopy and X-ray diffraction. The reaction of MeSiCl3 with three equivalents of LiC5H4(CO)(2)Fe-eta(1),eta(5)-C5H4Mn(CO)(2)PPh3 gave the hexanuclear complex MeSi[C5H4(CO)(2)Fe-eta(1),eta(5)-C5H4Mn(CO)(2)PPh3](3).