Cluster chemistry. V. Reactions between [Ru₃(CO)₁₁(CNBu^t)] and [Pt(η-C₂H₄)(PPh₃)₂] and related chemistry : Crystal and molecular structures of Di-μ-carbonyl-[μ-carbonyl-bis {(triphenylphosphine)platinum}]dicarbonyl(triphenylphosphine)ruthenium(2Ru-Pt)(Pt-Pt), [RuPt₂(CO)₅(PPh₃)₃], and its benzene solvate

Abstract

The reaction between [Ru₃(CO)₁₁(CNBu^t)] and [Pt(η-C₂H₄)(PPh₃)₂] at -30° affords a thermally unstable intermediate complex (A), which decomposes at room temperature affording, inter alia, [Ru₂Pt(CO)₇(PPhd₃)₃ (1), [RuPt₂(CO)₅(PPh₃)₃] (2), [RuPt₂(CO)₆(CNBu^t)(PPh₃)] (5) and [Ru₂Pt₂- (CO)₉(CNBu^t)(PPh₃)] (6). The hexanuclear complexes [Ru₂Pt₄(CO)_5-n(CNBu^t)(PPh₃)_4+n] [n = 0 (17) and 1 (18)] are obtained, with [Ru₂Pt(CO)₅(CNBu^t)(PPh₃)₄] (16), from reactions at 80°. Related Ru₂Pt and RuPt, complexes are obtained from reactions between complex (A) and CO, CNBu^t, Pme₃, P(C₆H₄Me-p)₃, or P(OMe)₃; related reactions between [Ru₃(CO)₁₁(CNBu^t)] and [Pt{P(C₆H₄Me-p)₃}₄], and between [Ru₃(CO)₁₀(CNBu^t)₂] and [Pt(η-C₂H₄)(PPh₃)₂, are also described.

The crystal structure of [RuPt₂(CO)₅(PPh₃)₃] has been determined by single-crystal X-ray diffraction methods at 295(1) K and refined by least squares to a residual of 0.035 for 6774 'observed' reflections. Crystals are triclinic, P 1, a 15.893(5), b 15.400(5), c 12.651(4) Ǻ, α 57.04(2), β 77.09(3), γ 84.10(3)°, Z 2. Crystals of the dibenzene solvate of the complex are monoclinic, P 2₁/c, a 11.868(4), b 18.647(8), c 29.24(1) A, β 98.35(3)°, Z 4, the structure being refined to a residual of 0.057 for 4530 'observed' reflections. Ligand dispositions are compared in detail with those observed in the analogous compound previously described with the methyldiphenylphosphine Iigand.