91281-79-7

Upstream product

• 33361-89-6 tetrakis(dimethylphenylphosphine)platinum⁽⁰⁾ 
• 82093-50-3 Os4(CO)12(μ3-S)2 
• 91281-77-5 Os4(CO)12(PMe2Ph)(μ3-S)2 

Relevant academic research and scientific papers

Cluster synthesis. 11. Role of sulfido ligands in the synthesis of heteronuclear clusters. Synthesis and crystal and molecular structures of PtOs4(CO)11(PMe2Ph)2(μ 3-S)2 and PtOs3(CO)9(PMe2Ph)2(μ 3-S)2

The synthesis of the mixed-metal cluster compounds PtOs4(CO)11(PMe2Ph)2(μ 3-S)2 (1) and PtOs3(CO)9(PMe2Ph)2(μ 3-S)2 (2) was achieved by the reaction of Os4(CO)12(μ3-S)2 (3) with Pt(PMe2Ph)4. Compound 1 was converted into 2 by treatment with CO. Compound 2 was also synthesized by the reaction of Os3(CO)9(μ3-S)2 with Pt(PMe2Ph)4. Compounds 1 and 2 were characterized structurally by single-crystal X-ray diffraction analyses. For 1: space group Pca21, No. 29; a = 23.801 (3) A?, b = 9.136 (3) A?, c = 18.368 (4) A?, Z = 4, ρcalcd = 2.81 g/cm3. The structure was solved by direct methods (MULTAN) and refined (2343 reflections, F2 ≥ 3.0σ(F2)) to the final residuals RF = 0.040 and RwF = 0.042. For 2: space group P21/c, No. 14; a = 9.533 (4) A?, b = 15.580 (7) A?, c = 24.547 (8) A?, β = 99.87 (3)°, Z = 4, ρcalcd = 2.51 g/cm3. The structure was solved by direct methods (MULTAN) and refined (2527 reflections, F2 ≥ 3.0σ(F2)) to the final residuals RF = 0.037 and RwF = 0.049. The cluster of 1 consists of a butterfly tetrahedron of four osmium atoms with a Pt(PMe2Ph)2 group bridging one of the peripheral edges. The cluster of 2 consists of an open triangular cluster of three osmium atoms with a Pt(PMe2Ph)2 group bridging one of the two osmium-osmium bonds. Variable-temperature 1H NMR studies of 2 showed that it undergoes a rapid rearrangement of the cluster framework, ΔG167 = 7.5 kcal/mol, that produces a time-averaged plane of symmetry. A process in which the platinum atom interchanges bridging sites between the two osmium-osmium bonds is proposed.

Ligand substitution reactons in electron-rich clusters. the synthesis, structures, and bonding of Os4(CO)12L(μ3-S)2 and Os4(CO)11L(μ3-S)2 (L = PMe2Ph and CN-t-Bu)

The compounds Os4(CO)12L(μ3-S)2 (2a, L = PMe2Ph; 2b, L = CN-t-Bu) have been synthesized by ligand addition to Os4(CO)12(μ3-S)2 (1). Both compounds have been characterized by single-crystal X-ray diffraction analyses. For 2a: space group P21/a, a = 17.941 (8) A?, b = 8.957 (3) A?, c = 17.949 (7) A?, β= 99.75 (4)°, Z = 4, ρcalcd = 3.04 g/cm3. The structure was solved by direct methods and refined (3542 reflections) to the final values for the residuals RF = 0.041 and RwF = 0.046. For 2b: space group P21/n, a = 15.113 (6) A?, b = 10.798 (9) A?, c = 18.659 (6) A?, β= 102.33 (3)°, Z = 4, ρcalcd = 2.87 g/cm3. The structure was solved by direct methods and refined (1939 reflections) to the final values of the residuals RF = 0.047 and RwF = 0.050. Both 2a and 2b contain open-planar clusters of four osmium atoms with three metal-metal bonds. Triply bridging sulfido ligands are symmetrically disposed on each side of the Os4 plane. When heated to 125°C, 2a and 2b lose CO and are converted in high yield to Os4(CO)11L(μ3-S)2 (3a, L = PMe2Ph; 3b, L = CN-t-Bu). 3a and 3b were both characterized by single-crystal X-ray diffraction analyses. For 3a: space group P1, a = 8.994 (5) A?, b = 10.057 (3) A?, c = 15.048 (7) A?, α = 99.62 (4)°, β = 92.22 (4)°, γ = 92.55 (5)°, Z = 2, ρcalcd = 3.15 g/cm3. The structure was solved by the heavy-atom method and refined (3110 reflections) to the final values of the residuals RF = 0.040 and RwF = 0.046. For 3b: space group Pbca, a = 23.819 (15) A?, b = 11.524 (10) A?, c = 18.497 (9) A?, Z = 8, ρcalcd = 3.18 g/cm3. The structure was solved by direct methods and refined (1815 reflections) to the final values of the residuals RF = 0.042 and RwF = 0.039. 3a and 3b both contain butterfly tetrahedral clusters of four metal atoms with triply bridging sulfido ligands on the two open-triangular faces. In both compounds two of the five metal-metal bonds are elongated, but in 3a they are nearly equal in length, 2.987 (1) and 3.013 (1) A?, while in 3b they are significantly different length, 2.965 (1) and 3.115 (1) A?.