Cluster synthesis. 11. Role of sulfido ligands in the synthesis of heteronuclear clusters. Synthesis and crystal and molecular structures of PtOs4(CO)11(PMe2Ph)23-S)2 and PtOs3(CO)9(PMe2Ph)23-S)2

Richard D. Adams, I. Horváth, Suning Wang

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Abstract

The synthesis of the mixed-metal cluster compounds PtOs4(CO)11(PMe2Ph)23-S)2 (1) and PtOs3(CO)9(PMe2Ph)23-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.

Original languageEnglish
Pages (from-to)1617-1623
Number of pages7
JournalInorganic Chemistry
Volume25
Issue number10
Publication statusPublished - 1986

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Osmium
osmium
Molecular structure
molecular structure
Crystal structure
Ligands
ligands
crystal structure
synthesis
Atoms
atoms
Interchanges
metal clusters
Platinum
tetrahedrons
platinum
Metals
Nuclear magnetic resonance
Single crystals
X ray diffraction

ASJC Scopus subject areas

  • Inorganic Chemistry

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@article{10fc64c00446419d874770acde2eff4d,
title = "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",
abstract = "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) {\AA}, b = 9.136 (3) {\AA}, c = 18.368 (4) {\AA}, 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) {\AA}, b = 15.580 (7) {\AA}, c = 24.547 (8) {\AA}, 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.",
author = "Adams, {Richard D.} and I. Horv{\'a}th and Suning Wang",
year = "1986",
language = "English",
volume = "25",
pages = "1617--1623",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "10",

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TY - JOUR

T1 - 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

AU - Adams, Richard D.

AU - Horváth, I.

AU - Wang, Suning

PY - 1986

Y1 - 1986

N2 - 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) 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.

AB - 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) 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.

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