Miklos. Tasi

Synthesis and reactivity of sulfido ruthenium carbonyl clusters

A survey of the structures and reactivity of ruthenium carbonyl cluster complexes containing sulfido ligands is presented and discussed.

Cluster synthesis—XX. The synthesis and crystal and molecular structure of Ru6(CO)17(μ4-η2-HC2Ph)(μ4-S)

Abstract The reaction of Ru5(CO)15(μ4-S) with HC2Ph at 68°C has resulted in the formation of the complex Ru5(CO)13(μ-CO)(μ4-η2-HC2Ph)(μ4-S), 1 in 60% yield. Compound 1 was found to react with Ru(CO)5 at 80°C to yield the enlarged cluster Ru6(CO)17(μ4-η2-HC2Ph)(μ4-S), 2 in 53% yield. Compound 2 was characterized structurally. Crystal data : Ru6SO17C25H6, M = 1216.80, monoclinic, P21/c (No. 14), a = 11.050(2), b = 22.503(5), c = 29.26(1) A, β = 90.80(3)°, V = 7276(4) A3, Dc = 2.27 g cm−3, Z = 8, λ(Mo-Kα) = 0.71073 A (graphite monochromator) μ = 24.9 cm−1. Methods: MITHRIL difference Fourier, full-matrix least-squares. Refinement of 4647 reflections (F2 ⩾ 3σ(F2)), (1°

The reactions of Mo2Ru(CO)7Cp2(η3-S) with phenylacetylene and Ru(CO)5

Abstract The reactivity of the heteronuclear cluster complex Mo2Ru(CO)7Cp2(η3-S) (1) toward HC2Ph was investigated and compared with the reactivity of the homonuclear complexes Ru3(CO)10(μ3-S) (2) and [Mo(CO)2Cp]2 (3). The reaction of 1 with HC2Ph yielded the new compound Mo2Ru(CO)2Cp2[μ3-η6-HCC(Ph)CHC(Ph)CHC(Ph)](μ3-S) (6), 15%. The compound contains a 1,3,5-triphenyldimetallahexatrienyl ligand formed by the head-to-tail coupling of three HC2Ph molecules. The C6-chain bridges one face of the triangular cluster. Three of the carbon atoms of the chain are π-bonded to one molybdenum atom. The other three carbon atoms are π-bonded to the ruthenium atom. The two ends of the chain are σ-bonded to the second molybdenum atom. When treated with CO at 100°C/25 atm, 6 eliminates 1,3,5,triphenylbenzene and reforms 1. At 125°C under nitrogen, the C6-chain in 6 is split at the C(3)C(4) bond to yield the two isomeric products Mo2Ru(CO)2Cp2[μ3-η3-HCC(Ph)CH][μ-η3-PhCC(H)CPh](μ3-S) (7) and Mo2Ru(CO)2Cp2[μ3-η3-HCC(Ph)CH][μ-η3-PhCC(Ph)CH](μ2-S) (8). Both products contain two dimetallaallyl ligands. One bridges the face of the cluster. The other bridges the MoMo edge. Compound 7 is converted into 8 at 125°C. When 1 is treated with Me3NO and HC2Ph at 25°C, the compound Mo2Ru(CO)5Cp2[μ-η4-PhCC(H)CC(H)Ph](μ3-S) (9) is formed in 11% yield. Compound 9 consists of an open cluster with a PhCC(H)CC(H)Ph ligand that bridges the open edge of the cluster. The four-carbon chain is π-bonded to a molybdenum atom while one carbon serves as the bridging link by bonding to the ruthenium atom. Compound 9 does not appear to be an intermediate en route to 6. When 1 is treated with Ru(CO)5 at 80°C, two higher nuclearity cluster products Mo2Ru4(CO)13(μ4-η2-CO)Cp2(μ4-S) (10) and Mo2Ru5(CO)14(μ4-η2-CO)2Cp2(μ4-S) (11) are formed. Compound 10 consists of a square pyramidal Mo2Ru4 cluster containing a quadruply bridging sulphido ligand on the square base. An Ru(CO)3 group bridges an RuRu edge of the square base. A dihapto quadruply bridging carbonyl ligand is bonded by its carbon atom to an MoRu2 triangle of the square pyramid and is bonded by its oxygen atom to the Ru(CO)3 group. Compound 11 is similar to 10 but has an additional Ru(CO)3 group bridging the second RuRu basal edge of the cluster and also has a second dihapto quadruply bridging carbonyl ligand. IR spectra show that the two quadruply bridging carbonyl ligands are vibrationally coupled by the appearance of two CO stretching absorptions at 1419 and 1453 cm−1. When 10 is heated to 80°C, it is converted to an isomer 12 by shifting the quadruply bridged carbonyl ligand to a terminal bonding mode. The cluster is transformed from an edge bridging form in 10 to a face capped form in 12.

Das Metallcarbonyl OsCo2(CO)11: Verbesserte Darstellung und einige Reaktionen / The Metal Carbonyl OsCo2(CO)11: Improved Synthesis and Some Reactions

Of several methods tested to improve the yield of the metal carbonyl OsCo2(CO)11 (1), the reaction of H2Os(CO)4 with Co2(CO)6μ-C2H2) was found to give the best results (>50%). The availability of 1 allowed to study its capping reactions with C2H4S, PhPH2 and alkynes RC≡CH leading to the products OsCo2(CO)9(μ3-X) for X = S (2), PPh (3), and RC=CH (4). The capped clusters are thermally more stable than the corresponding RuCo2(CO)9 derivatives, and the alkyne capped species are more difficult to transform to the vinylidene capped clusters OsCo2(CO)9(μ3-C=CHR) (5) than the analogous RuCo2 species.