Reaction of the lithoxy phosphaalkyne (DME) 2 LiOCtP (1) with 1 equiv of the complexes 3a-c) as red amorphous solids in 32-37% yield. By treatment with ((Z)-cyclooctene)-Cr(CO) 5 , compound 3a was converted into the red complex Cp*(CO) 2 FeP[Cr(CO) 5 ]C(O)P-[Fe(CO) 2 Cp*]C(O) (4). Constitutions and configurations of 3a-c and 4 were determined by elemental analyses and spectra (IR, 1 H, 13 C, and 31 P NMR, MS). The molecular structure of 4 was established by a single-crystal X-ray analysis.