| Abstract: The substituted reactions of (μ-FcC≡CH)Co2(CO)6 with PPh3, AsPh3 and dppm have been studied and three new substituted derivatives have been obtained. The compounds were characterized by elemental analysis, IR, 1H NMR, MS and X-ray crystallography. They have the following formula: (μ-FcC≡CH)Co2(CO)6-nL[n=1, L=PPh3（2）, AsPh3（3）; n=2, L=dppm (4)]. The cluster 2 crystallizes in monoclinic, space group P21/n, with a=1.342 4(8) nm, b=1.305 4(8) nm, c=1.875 0(9) nm, β=103.084(9)°, V=3.201(3) nm3, Z=4, F(000)=1 480, Dc=1.515 g·cm-3, μ=15.62 cm-1; final R indices [I > 2σ(I)]: R1=0.040 9, ωR2=0.076 9; S=1.007, Δρmax=463e·nm-3, Δρmin=-395 e·nm-3. The cluster 3 crystallizes in monoclinic, space group P21/n, with a=1.341 0(4) nm, b=1.307 9(4) nm, c=1.912 0(5) nm, β=103.043(5)°, V=3.267(15) nm3, Z=4, F(000)=1 552, Dc=1.574 g·cm-3, μ=24.87 cm-1; final R indices[I> 2σ（I）]：R1=0.0437, ωR2=0.078 2; S=0.995, Δρmax=530 e·nm-3, Δρmin=-444 e·nm-3. CCDC: 221860, 2; 221863, 3. |
