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(μ3-S)2 and PtOs3(CO)9(PMe2Ph)2(μ3-S)2

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review

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Original languageEnglish
Pages (from-to)1617-1623
Journal / PublicationInorganic Chemistry
Volume25
Issue number10
Publication statusPublished - 1 May 1986
Externally publishedYes

Abstract

The synthesis of the mixed-metal cluster compounds PtOs4(CO)11(PMe2Ph)2(μ3-S)2 (1) and PtOs3(CO)9(PMe2Ph)2(μ3-S)2 (2) was achieved by the reaction of Os4(CO)123-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)93-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) Å, b = 9.136 (3) Å, c = 18.368 (4) Å, 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) Å, b = 15.580 (7) Å, c = 24.547 (8) Å, 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. © 1986 American Chemical Society.

Citation Format(s)

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(μ3-S)2 and PtOs3(CO)9(PMe2Ph)2(μ3-S)2. / Adams, Richard D.; Horváth, István T.; Wang, Suning.

In: Inorganic Chemistry, Vol. 25, No. 10, 01.05.1986, p. 1617-1623.

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review