Synthesis of some phosphino- and arsinobenzenechromium tricarbonyl derivatives and metal carbonyl clusters

Article abstract of DOI:10.1139/v96-244

The synthesis of a number of new phosphino- and arsinobenzenechromium tricarbonyl ligands ER₂C₆H₅Cr(CO)₃ (ER₂ = PEt₂, PPrⁱ₂;, PBu^t₂, PPh₂, AsPh₂ AsMe₂), ER[C₆H₅Cr(CO)₃]₂ (ER = PEt, PBu^t, PPh, AsPh) has been achieved by reacting lithium derivatives of benzenechromium tricarbonyl with appropriate chlorophosphines or iodoarsines. The spectroscopic properties of these ligands are described. The structure of Prⁱ₂PC₆H₅Cr(CO)₃ was determined by an X-ray crystallographic study. This is the first solid state structure to be reported for a phosphinobenzenechromium tricarbonyl derivative. The structures of four metal carbonyl cluster complexes were also determined. Crystals of Prⁱ₂PC₆H₅Cr(CO)₃ (3, C₁₅H₁₉CrO₃P) are monoclinic, space group P2₁/c, a = 8.150(2) A, b = 13.490(2) A, c = 15.125(1) A, β = 100.19(1)°, Z = 4; those of Ru₃(CO)₁₁[PPrⁱ₂C₆H ₅Cr(CO)₃] (15, C₂₆H₁₉CrO₁₄PRu₃) are monoclinic, space group P2₁/n, a = 8.565(2) A, b = 21.808(3) A, c = 17.167(3) A, β = 97.41 (2)°, Z = 4; those of Ru₃(CO)₁₀[PPh₂C₆H ₅Cr(CO)₃]₂ (19, C₃₂H₁₅CrO₁₄PRu₃) are orthorhombic, space group Pbca, a = 17.367(4) A, b = 24.471(5) A, c = 16.096(3) A, Z = 8; those of Ru₃(CO)₁₀[PPrⁱ₂C₆H ₅Cr(CO)₃]₂·CH₂Cl₂ (16, C₄₀H₃₈Cr₂O₁₆P₂Ru ₃·CH₂Cl₂) are orthorhombic, space group P2₁2₁2, a = 13.832(3) A, b = 17.558(2) A, c = 10.144(1) A, Z = 2; and those of Os₃(CO)₉[PEt₂C₆H ₅Cr(CO)₃]₃ (26, C₄₈H₄₅Cr₃O₁₈Os₃P ₃) are trigonal, space group P3, a = 15.7558(4) A, c = 12.662(1) A, Z = 2. The structures were solved by the Patterson method and were refined by full-matrix least-squares procedures to R = 0.031, 0.027, 0.029, 0.025, and 0.029 (R_w = 0.027, 0.024, 0.024, 0.023, and 0.025) for 2326, 4110, 3878, 3046, and 4093 reflections with I ≥ 3σ(7), respectively.