Multinuclear complexes derived from ferrocenylphosphines and triruthenium dodecacarbonyl

Article abstract of DOI:10.1021/om00021a036

Pyrolysis of Ru₃(CO)₁₁(PFc₂Ph) in hexanes for 15 h gave the trinuclear cluster Ru₃(CO)₈-(μ-CO)(μ-H)[μ-η ³-(η⁵-C₅H₃PFcPh)Fe(η ⁵-C₅H₅)] (11) in 20% yield. Pyrolysis of Ru₃(CO)₁₂ with PFc₂Ph in octane for 3.5 h gave the tetranuclear cluster Ru₄(CO)₁₁(μ₃-PFc)(μ-η ¹:η⁵-C₅H₄ (12) in 12% yield and the previously known 8, Ru₄(CO)₁₀(μ-CO)μ₄-PFc)(μ ₄-C₆H₄), in 10% yield: the mild conditions are noteworthy. Pyrolysis of Ru₃(CO)₁₂ with PEt₂Fc in octane for 18 h gave the hexanuclear cluster complexes Ru₆C(CO)₁₄(μ-PEt₂)₂ (13) and Ru₆C(CO)₁₃(μ-PEt₂)-(η⁵-C ₅H₅) (14) in 15% and 25% yields, respectively, and the pentanuclear derivative Ru₅-(CO)₉(μ-CO)(η⁶-C₆H ₆)₂(μ₄-PEt) (15) (low yield). Pyrolysis of Ru₃(CO)₁₂ with PEtFc₂ in toluene for 10 h gave the pentanuclear cluster Ru₅(CO)₁₂(μ₄-PEt)(η⁶-C ₇H₈) (16) in ～5% yield. Crystal data: 8, monoclinic, space group P2₁/c, a = 14.725(3) A?, b = 9.024(2) A?, c = 22.719(1) A?, β = 92.078(8)°, Z = 4; 11, triclinic, P1, a = 12.7671(9) A?, b = 13.284(1) A?, c = 10.2212(8) A?, α = 93.006(6)°, β = 98.561(6)°, γ = 83.665(6)°, Z = 2; 12, monoclinic, space group P2₁/c, a = 10.463(2) A?, b = 16.412(1) A?, c = 17.903(2) A?, β = 103.85(1)°, Z = 4; 13, monoclinic, space group C2/c, a = 12.566(2) A?, b = 16.326(2) A?, c = 17.001(2) A?, β = 105.43(1)°, Z = 4; 14, monoclinic, space group P2₁/c,a = 12.638(2) A?, b = 9.911(3) A?, c = 24.743(5) A?, β = 91.33-(2)°, Z = 4; 15, orthorhombic, space group Cmc2₁, a = 16.239(1) A?, b = 13.754(2) A?, c = 11.895(2) A?, Z = 4; 16, monoclinic, space group C2/c, a = 31.831(3) A?, b = 9.904(2) A?, c = 17.536(2) A?, β = 99.36(1)°, Z = 8. The structures were solved by direct or Patterson methods and were refined by full-matrix least-squares procedures to R = 0.042, 0.024, 0.027, 0.024, 0.028, 0.032, and 0.026 for 4943, 8583, 5279, 3650, 6357, 1302, and 5711 reflections with I ≥ 3σ(I), respectively.