Abstract
The reactions between MCH 2 CCCHCH 2 (M = CpW(CO) 3 (1), Mn(CO) 5 (2)) and Co 2 (CO) 8 in THF at 0 °C afforded Co(CO) 3 [μ 2 -CpW(CO) 3 CH 2 CCCHCH 2 ]Co(CO) 3 (3) and MnCo 2 (CO) 10 (μ 3 -η 1 :η 3 :η 3 -CH 2 CCCHCH 2 ) (4), respectively. The dinuclear 2-butyne-1,4-di-yl compounds MCH 2 CCCH 2 M (M = CpW(CO) 3 (5); Cp*W(CO) 3 (6), Cp* = C 5 Me 5 ) have been prepared. Under flowing CO, the reactions of 5 and 6 with Fe 2 (CO) 9 afforded the maleoyl compounds [formula omitted] in excellent yields. Under nitrogen, a similar reaction of 5 with Fe 2 (CO) 9 produced two additional trinuclear clusters Cp 2 W 2 Fe(CO) 8 (μ 3 -η 1 :η 2 :η 3 -CH 2 CCCH 2 ) (9) and CpWFe 2 (CO) 8 (μ 3 -η 1 η 2 :η 2 -CH 2 CCCH 3 ) (10) in addition to 7. In contrast, 6 reacted with Fe 2 (CO) 9 in the absence of CO to give 8 as the only product. The reactions of 5 and 6 with Co 2 (CO) 8 gave the tetranuclear compounds [formula omitted]. The molecular structures of 4, 8, 9, and 12 were determined by X-ray diffraction study to have the following parameters: for 4, space group P1̅, a = 8.427 (3) Å, b = 9.326 (2) Å, c = 12.534 (4) Å, α = 97.31 (2)°, β = 87.76 (3)°, γ = 110.80 (2)°, Z = 2, R = 0.029 and R w = 0.043; for 8, space group C2/c, a = 47.984 (7) Å, b = 8.478 (2) Å, c = 19.883 (6) Å, β = 107.60 (2)°, Z = 8, R = 0.053, and R w = 0.042; for 9, space group P1̅, a = 7.810 (2) Å, b = 10.889 (4) Å, c = 13.970 (5) Å, α = 110.96 (3)°, β = 95.20 (2)°, γ = 93.72 (2)°, Z = 2, R = 0.032, and R w = 0.031; for 12, space group C2/c, a = 20.267 (3) Å, b = 24.628 (3) Å, c = 8.816 (4) Å, β = 99.68 (2)°, Z = 4, R = 0.031, and R w = 0.069. © 1993, American Chemical Society. All rights reserved.