Synthesis of trinuclear mixed-metal clusters Os2Fe(CO)10L2 (L = OH, I, CO). The crystal structures of Os2Fe(CO)10(μ-OH)2 and Os2Fe(CO)12 · 0.41Os3(CO)12

Article abstract of DOI:10.1016/S0022-328X(96)06957-4

The heterometallic clusters Os₂Fe(CO)₁₀(μ-X)₂ (X = OH, I) were obtained from the binuclear osmium complexes Os₂(CO)₆X_n (X = Cl, n = 4; X = I, n = 2). The structure of Os₂Fe(CO)₁₀(μ-OH)₂ was determined by a single-crystal X-ray diffraction analysis. The crystal is triclinic and crystallizes in the space group P1 and a = 14.009(6), b = 13.330(4), c = 9.511(2) A, α = 103.69(2), β = 81.83(3), γ = 102.22(3)°, V = 1699(1) A³, Z = 4, D_calc = 2.969 g cm^-3, R = 0.093 for 2359 independent reflections (F_o > 6σ(F_o)). The cluster consists of an open triangular OsFeOs metal core with no Os-Os bond. The bridging OH groups are coordinated semiaxially and span the Os-Os edge. On heating in the presence of an excess of Fe₂(CO)₉, the Os₂Fe(CO)₁₀(μ-I)₂ cluster is converted to Os₂Fe(CO)₁₂. The co-crystallate Os₂Fe(CO)₁₂ · 0.41Os₃(CO)₁₂ was isolated from the solution of Os₂Fe(CO)₁₀(μ-I)₂, as the product of decomposition of the initial cluster. It crystallizes in the monoclinic system, space group P2₁/n, with a = 8.056(2), b = 14.743(2), c = 14.520(2) A, β = 100.62(1)°, V = 1695.0(5) A³, Z = 4, D_calc = 3.179 g cm^-3 and R = 0.0250 for 1997 independent reflections (F_o > 4σ(F_o)).