Cluster synthesis. 1. The use of sulfido ligands in the synthesis of high nuclearity transition-metal cluster compounds. The synthesis and crystal and molecular structures of Os6(CO)174-S)2 and Os6(CO)164-S)(μ3-S)

Richard D. Adams, I. Horváth, Li Wu Yang

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Abstract

By taking advantage of the multicoordination and donor capacity of sulfido ligands, the clusters Os3(CO)93-S)2 (I) and Os3(CO)10(NCMe)2 (II) have been combined by reaction to yield the high nuclearity cluster OS6(CO)174-S)2 (III). III has been characterized by X-ray crystallographic methods: space group P212121, a = 11.280 (5) Å, b = 14.622 (8) Å, c = 17.626 (5) Å, V = 2907 (4) Å3, Z = 4, ρcalcd = 3.84 g/cm3. A total of 1726 reflections (F2 ≥ 2.0σ(F2)) produced the final residuals R1 = 0.037 and R2 = 0.030. III consists of a pentagonal-bipyramidal cluster that includes five osmium atoms and two sulfido ligands with the sulfido ligands in equatorial sites. An Os(CO)4 group bridges an edge of the cluster between apical and equatorial metal atoms. The apical-equatorial metal-metal bond distances in the cluster, which range from 2.898 (2)-2.988 (2) Å, are significantly longer than the one equatorial-equatorial bond distance at 2.833 (2) Å. When refluxed in octane solvent for 5 h, III loses 1 mol of CO and is transformed into new cluster complex Os6(CO)164-S)(μ3-S) (IV). IV has also been analyzed by X-ray diffraction methods: space group P21/c, a = 10.083 (4) Å, b = 12.633 (4) Å, c = 21.383 (4) Å, β = 91.73 (2)°, V = 2722 (3) Å3, Z = 4, ρcalcd = 4.03 g/cm3. A total of 2629 reflections (F2 ≥ 2.0σ(F2)) produced the final residuals R1 = 0.038 and R2 = 0.039. IV contains a square-pyramidal cluster of five metal atoms with a quadruply bridging sulfido ligand spanning the square base. The sixth metal atom bridges an edge of the square base and that group of three contains a triply bridging sulfido ligand. This edge of the square base contains an unusually short metal-metal bond (2.686 (1) Å), which could be due to the fact that it contains four single atom bridges. The formation of III from the trinuclear units of I and II is described, as well as the transformation of III into IV. Via their adaptable, multicoordination character, the sulfido ligands play a major role in the initial linking of the trinuclear units and the subsequent reorganization of the metal-metal bonding.

Original languageEnglish
Pages (from-to)1533-1538
Number of pages6
JournalJournal of the American Chemical Society
Volume105
Issue number6
Publication statusPublished - 1983

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Molecular Structure
Molecular structure
Transition metals
Crystal structure
Metals
Ligands
Atoms
Osmium
X-Ray Diffraction
X-Rays
X ray diffraction
X rays

ASJC Scopus subject areas

  • Chemistry(all)

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@article{8f5870b362704246a137fa4f49e652bc,
title = "Cluster synthesis. 1. The use of sulfido ligands in the synthesis of high nuclearity transition-metal cluster compounds. The synthesis and crystal and molecular structures of Os6(CO)17(μ4-S)2 and Os6(CO)16(μ4-S)(μ3-S)",
abstract = "By taking advantage of the multicoordination and donor capacity of sulfido ligands, the clusters Os3(CO)9(μ3-S)2 (I) and Os3(CO)10(NCMe)2 (II) have been combined by reaction to yield the high nuclearity cluster OS6(CO)17(μ4-S)2 (III). III has been characterized by X-ray crystallographic methods: space group P212121, a = 11.280 (5) {\AA}, b = 14.622 (8) {\AA}, c = 17.626 (5) {\AA}, V = 2907 (4) {\AA}3, Z = 4, ρcalcd = 3.84 g/cm3. A total of 1726 reflections (F2 ≥ 2.0σ(F2)) produced the final residuals R1 = 0.037 and R2 = 0.030. III consists of a pentagonal-bipyramidal cluster that includes five osmium atoms and two sulfido ligands with the sulfido ligands in equatorial sites. An Os(CO)4 group bridges an edge of the cluster between apical and equatorial metal atoms. The apical-equatorial metal-metal bond distances in the cluster, which range from 2.898 (2)-2.988 (2) {\AA}, are significantly longer than the one equatorial-equatorial bond distance at 2.833 (2) {\AA}. When refluxed in octane solvent for 5 h, III loses 1 mol of CO and is transformed into new cluster complex Os6(CO)16(μ4-S)(μ3-S) (IV). IV has also been analyzed by X-ray diffraction methods: space group P21/c, a = 10.083 (4) {\AA}, b = 12.633 (4) {\AA}, c = 21.383 (4) {\AA}, β = 91.73 (2)°, V = 2722 (3) {\AA}3, Z = 4, ρcalcd = 4.03 g/cm3. A total of 2629 reflections (F2 ≥ 2.0σ(F2)) produced the final residuals R1 = 0.038 and R2 = 0.039. IV contains a square-pyramidal cluster of five metal atoms with a quadruply bridging sulfido ligand spanning the square base. The sixth metal atom bridges an edge of the square base and that group of three contains a triply bridging sulfido ligand. This edge of the square base contains an unusually short metal-metal bond (2.686 (1) {\AA}), which could be due to the fact that it contains four single atom bridges. The formation of III from the trinuclear units of I and II is described, as well as the transformation of III into IV. Via their adaptable, multicoordination character, the sulfido ligands play a major role in the initial linking of the trinuclear units and the subsequent reorganization of the metal-metal bonding.",
author = "Adams, {Richard D.} and I. Horv{\'a}th and Yang, {Li Wu}",
year = "1983",
language = "English",
volume = "105",
pages = "1533--1538",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "6",

}

TY - JOUR

T1 - Cluster synthesis. 1. The use of sulfido ligands in the synthesis of high nuclearity transition-metal cluster compounds. The synthesis and crystal and molecular structures of Os6(CO)17(μ4-S)2 and Os6(CO)16(μ4-S)(μ3-S)

AU - Adams, Richard D.

AU - Horváth, I.

AU - Yang, Li Wu

PY - 1983

Y1 - 1983

N2 - By taking advantage of the multicoordination and donor capacity of sulfido ligands, the clusters Os3(CO)9(μ3-S)2 (I) and Os3(CO)10(NCMe)2 (II) have been combined by reaction to yield the high nuclearity cluster OS6(CO)17(μ4-S)2 (III). III has been characterized by X-ray crystallographic methods: space group P212121, a = 11.280 (5) Å, b = 14.622 (8) Å, c = 17.626 (5) Å, V = 2907 (4) Å3, Z = 4, ρcalcd = 3.84 g/cm3. A total of 1726 reflections (F2 ≥ 2.0σ(F2)) produced the final residuals R1 = 0.037 and R2 = 0.030. III consists of a pentagonal-bipyramidal cluster that includes five osmium atoms and two sulfido ligands with the sulfido ligands in equatorial sites. An Os(CO)4 group bridges an edge of the cluster between apical and equatorial metal atoms. The apical-equatorial metal-metal bond distances in the cluster, which range from 2.898 (2)-2.988 (2) Å, are significantly longer than the one equatorial-equatorial bond distance at 2.833 (2) Å. When refluxed in octane solvent for 5 h, III loses 1 mol of CO and is transformed into new cluster complex Os6(CO)16(μ4-S)(μ3-S) (IV). IV has also been analyzed by X-ray diffraction methods: space group P21/c, a = 10.083 (4) Å, b = 12.633 (4) Å, c = 21.383 (4) Å, β = 91.73 (2)°, V = 2722 (3) Å3, Z = 4, ρcalcd = 4.03 g/cm3. A total of 2629 reflections (F2 ≥ 2.0σ(F2)) produced the final residuals R1 = 0.038 and R2 = 0.039. IV contains a square-pyramidal cluster of five metal atoms with a quadruply bridging sulfido ligand spanning the square base. The sixth metal atom bridges an edge of the square base and that group of three contains a triply bridging sulfido ligand. This edge of the square base contains an unusually short metal-metal bond (2.686 (1) Å), which could be due to the fact that it contains four single atom bridges. The formation of III from the trinuclear units of I and II is described, as well as the transformation of III into IV. Via their adaptable, multicoordination character, the sulfido ligands play a major role in the initial linking of the trinuclear units and the subsequent reorganization of the metal-metal bonding.

AB - By taking advantage of the multicoordination and donor capacity of sulfido ligands, the clusters Os3(CO)9(μ3-S)2 (I) and Os3(CO)10(NCMe)2 (II) have been combined by reaction to yield the high nuclearity cluster OS6(CO)17(μ4-S)2 (III). III has been characterized by X-ray crystallographic methods: space group P212121, a = 11.280 (5) Å, b = 14.622 (8) Å, c = 17.626 (5) Å, V = 2907 (4) Å3, Z = 4, ρcalcd = 3.84 g/cm3. A total of 1726 reflections (F2 ≥ 2.0σ(F2)) produced the final residuals R1 = 0.037 and R2 = 0.030. III consists of a pentagonal-bipyramidal cluster that includes five osmium atoms and two sulfido ligands with the sulfido ligands in equatorial sites. An Os(CO)4 group bridges an edge of the cluster between apical and equatorial metal atoms. The apical-equatorial metal-metal bond distances in the cluster, which range from 2.898 (2)-2.988 (2) Å, are significantly longer than the one equatorial-equatorial bond distance at 2.833 (2) Å. When refluxed in octane solvent for 5 h, III loses 1 mol of CO and is transformed into new cluster complex Os6(CO)16(μ4-S)(μ3-S) (IV). IV has also been analyzed by X-ray diffraction methods: space group P21/c, a = 10.083 (4) Å, b = 12.633 (4) Å, c = 21.383 (4) Å, β = 91.73 (2)°, V = 2722 (3) Å3, Z = 4, ρcalcd = 4.03 g/cm3. A total of 2629 reflections (F2 ≥ 2.0σ(F2)) produced the final residuals R1 = 0.038 and R2 = 0.039. IV contains a square-pyramidal cluster of five metal atoms with a quadruply bridging sulfido ligand spanning the square base. The sixth metal atom bridges an edge of the square base and that group of three contains a triply bridging sulfido ligand. This edge of the square base contains an unusually short metal-metal bond (2.686 (1) Å), which could be due to the fact that it contains four single atom bridges. The formation of III from the trinuclear units of I and II is described, as well as the transformation of III into IV. Via their adaptable, multicoordination character, the sulfido ligands play a major role in the initial linking of the trinuclear units and the subsequent reorganization of the metal-metal bonding.

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