105121-22-0Relevant academic research and scientific papers
Cluster synthesis. 17. Synthesis and structural characterizations of Ru5(CO)15(μ4-S), Ru6(CO)18(μ4-S), and Ru7(CO)21(μ4-S)
Adams, Richard D.,Babin, James E.,Tasi, Miklos
, p. 503 - 513 (2008/10/08)
When Ru3(CO)9(μ3-CO)(μ3-S) (1) was heated to 68°C in the presence of Ru(CO)5, the three new higher nuclearity clusters Ru5(CO)15(μ4-S) (2), Ru6(CO)15(μ-CO)3(μ4-S) (3), and Ru7(CO)19(μ-CO)2(μ4-S) (4) were formed. 3 was also made by heating 2 with Ru(CO)5 to 98°C, and 4 was also made by heating 3 with Ru(CO)5 to 98°C. 2, 3, and 4 were degraded by treatment with CO (1 atm)/98°C by the stepwise removal of mononuclear ruthenium carbonyl groupings. Compounds 2, 3, and 4 were characterized structurally by single-crystal X-ray diffraction analyses. For 2: space group P21/c, a = 11.896 (3) A?, b = 28.956 (9) A?, c = 13.009 (5) A?, β = 90.59 (2)°, V = 4481 (2) A?3, Z = 8, ρcalcd = 2.84 g/cm3. The structure of 2 was solved by direct methods and was refined (4012 reflections) to the final values of the residuals, R = 0.030 and RwF = 0.029. For 3: space group P1, a = 17.505 (4) A?, b = 20.303 (5) A?, c = 9.047 (2) A?, α = 91.43 (2)°, β = 103.49 (2)°, γ = 67.20 (2)°, V = 2874 (1) A?3, Z = 4, ρcalcd = 2.64 g/cm3. The structure of 3 was solved by direct methods and was refined (6319 reflections) to the final values of the residuals, R = 0.037 and RwF = 0.041. For 4: space group P21/n, a = 12.485 (5) A?, b = 16.821 (5) A?, c = 16.208 (5) A?, β = 104.06 (3)°, V = 3302 (2) A?3, Z = 4, ρcalcd = 2.67 g/cm3. The structure of 4 was solved by direct methods and was refined (2747 reflections) to the final values of residues, R = 0.048 and RwF = 0.048. Each of the structures of 2, 3, and 4 consists of square-pyramidal cluster of five ruthenium atoms with a quadruply bridging sulfido lignd spanning the square base. Compound 2 contains two symmetry-independent molecules in the crystal, and they are structurally different in the arrangement of their carbonyl ligands. Molecule A contains four bridging carbonyl ligands, one on each edge of the square base of the cluster. Molecule B has three edge-bridging carbonyl ligands and one asymmetric triply bridging carbonyl ligand. Compound 3 is similar to molecule A of 2 but has a Ru(CO)4 group in place of one of the bridging CO ligands. Compound 4 is similar to molecule A of 2 but has two Ru(CO)4 groups substituted on opposite edges of the square base for the bridging CO ligands.
Cluster syntheses. 13. Chemistry of sulfidoruthenium carbonyl clusters. Synthesis and characterization of the new unsaturated clusters Ru4(CO)11-nLn(μ4-S)2 (n = 0-2, L = PMe2Ph)
Adams, Richard D.,Babin, James E.,Tasi, Miklos
, p. 4514 - 4519 (2008/10/08)
The compound Ru3(CO)9(μ3-CO)(μ3-S) (1) has been prepared by three methods: pyrolysis and photolysis of Ru3(CO)10(μ-SPh)(μ-H), in 89% and 80% yields, respectively, and the reaction of Ru3(CO)12 and ethylene sulfide in 67% yield. The compound Ru3(CO)9(μ3-S)2 (3) was prepared in 94% yield from the reaction of Ru3(CO)12 with an excess of ethylene sulfide. Compound 3 was also obtained from the reaction of 1 with ethylene sulfide in 97% yield. Compounds 1 and 3 react with hydrogen by loss of CO to form the compounds Ru3(CO)9(μ3-S)(μ-H)2 (2) and Ru3(CO)8(μ3-S)2(μ-H) 2 (4) in 92% and 48% yields, respectively. Compound 4 can be converted back into 3 by reaction with CO under 50 atm pressure in 94% yield. Compound 3 reacts with Ru(CO)5 in the presence of UV irradiation to form the tetraruthenium cluster Ru4(CO)9(μ-CO)2(μ4-S) 2 (5) in 90% yield. The reaction of 4 with PMe2Ph at 25°C yields the substitution products Ru4(CO)11-n(PMe2Ph)n(μ 4-S)2 (6, n = 1; 7, n = 2). The structure of 7 was established by a single-crystal X-ray diffraction analysis. Crystal data: space group, P21/n; a = 9.752 (2) A?; b = 20.471 (3) A?; c = 16.236 (2) A?; β = 93.04 (1)°; Z = 4; ρcalcd = 2.07 g/cm3. The structure was solved by direct methods and was refined (3843 reflections) to the final values of the residuals R = 0.027 and Rw = 0.031. The molecule consists of a square cluster of four ruthenium atoms with quadruply bridging sulfido ligands on the two square faces of the cluster. Two carbonyl ligands bridge adjacent edges of the square and produce a slight shortening of the two Ru-Ru bonds. The clusters of compounds 5 and 6 are believed to be structurally similar to 7. Compounds 5-7 contain 62 valence electrons and are therefore electron deficient by two electrons. They do, however, conform to the requirements of the polyhedral skeletal electron pair theory.
