Abstract
The reaction between M-CH <sub>2</sub> C≡CCH=CH <sub>2</sub> (M = CpW(CO) <sub>3</sub> (1), Mn(CO) <sub>5</sub> (2)) and Fe <sub>2</sub> (CO) <sub>9</sub> in hexane at 23 °C afforded M-CH <sub>2</sub> C(CO-Fe(CO) <sub>4</sub> -CO)C-CH=CH <sub>2</sub> (M = CpW(CO) <sub>3</sub> (3), Mn(CO) <sub>5</sub> (4)), MFe <sub>2</sub> (CO) <sub>e</sub> (μ <sub>3</sub> -η <sup>1</sup> , η <sup>3</sup> ,η <sup>3</sup> -CH <sub>2</sub> CCCH=CH <sub>2</sub> ) (M = CpW(CO) <sub>3</sub> (5), Mn(CO) <sub>6</sub> (7)), and CpWFe <sub>2</sub> (CO) <sub>8</sub> (μ <sub>3</sub> -η <sup>1</sup> , η <sup>2</sup> , η <sup>2</sup> -CH <sub>2</sub> CCCH=CH <sub>2</sub> ) (6). Under flowing CO, a similar reaction gave only 3 and 4 in high yields (>90%). Heating 1 with Fe <sub>3</sub> (CO) <sub>12</sub> in refluxing hexane produced 5 and 6. Treatment of 1 with Ru <sub>3</sub> (CO) <sub>10</sub> (CH <sub>3</sub> CN) <sub>2</sub> in CH <sub>3</sub> CN afforded CpWRu, (CO) <sub>8</sub> (μ <sub>3</sub> -η <sup>1</sup> , η <sup>2</sup> , η <sup>2</sup> , η <sup>2</sup> -CH <sub>2</sub> CCCH=CH <sub>2</sub> ) (8). Stirring of 1 with Os <sub>3</sub> (CO) <sub>10</sub> (CH <sub>3</sub> CN) <sub>2</sub> formed CpWO <sub>3</sub> (CO) <sub>13</sub> (μ <sub>4</sub> -η <sup>1</sup> , η <sup>1</sup> , η <sup>1</sup> , η <sup>2</sup> -CH <sub>2</sub> CCCH=CH <sub>2</sub> ) (9) and an unusual tetranuclear cluster of which one W-CO has formally migrated to the ligand β-carbon. The molecular structures of 3, 5, 8, and 10 have been determined by X-ray diffraction study to have the following parameters: for 3 space group P2 <sub>1</sub> /π, a = 9.9947 (21) Å, b = 9.4773 (19) Å, c = 21.845 (3) Å, β = 93.635 (15)°, Z = 4, R = 0.030, and R <sub>w</sub> = 0.023; for 5 space group triclinic, P1, a = 9.6100 (24) Å, b = 13.654 (4) Å, c = 8.4220 (23) Å, a = 100.215 (21)°, β = 104.394 (21)°, y = 92.978 (21)°, Z = 2, R = 0.024, and R <sub>w</sub> = 0.022; for 8 space group monoclinic, C <sub>2</sub> /c, o = 28.580 (5) Å, b = 9.285 (4) Å, c = 15.978 (4) Å, β = 110.062 (15)°, Z = 8, R = 0.046, and R <sub>w</sub> = 0.034; for 10 space group P2 <sub>1</sub> /n, a = 11.825 (7) Å, b = 10.057 (7) Å, c = 22.889 (13) Å, β = 92.97 (6)°, Z = 4, R = 0.055, and R <sub>w</sub> = 0.047 for 3060 reflections >2σ(I) out of 4763 unique reflections and 362 parameters. © 1991, American Chemical Society. All rights reserved.