Cleavage of carbon-sulfur bonds in thiolato ligands in osmium carbonyl cluster compounds. The synthesis and structural characterization of H2Os6(CO)184-S)(μ 3-S) and two isomers of H2Os6(CO)174-S)(μ 3-S)

Richard D. Adams, István T. Horváth, Pradeep Mathur, Brigitte E. Segmüller

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Abstract

Thermal degradation of HOs3(CO)10(μ-SCH2C6H 5), I, at 150°C leads to cleavage of the carbon-sulfur bond in the phenylmethanethiolato ligand by two competing processes. By one process the cleavage is followed by the elimination of toluene and the formation of the sulfidoosmium carbonyl clusters Os3-(CO)93-S)2, Os6(CO)164-S)(μ3-S), and Os7(CO)204-S)2. The second mechanism involves homolysis of the carbon-sulfur bond and formation of dibenzyl, the red hydride-containing hexanuclear cluster H2Os6(CO)174-S)(μ 3-S), III, and its green isomer IV. Both III and IV were characterized by X-ray crystallographic methods. For III: space group C2/c, a = 20.364 (5) Å, b = 9.764 (4) Å, c = 32.544 (7) Å, β = 114.01 (2)°, V = 5900 (6) Å3, Z = 8, ρcalcd = 3.79 g/cm3. The structure was solved by direct methods (MULTAN) and refined (2456 reflections, F2 ≥ 3.0σ(F2)) to the final values of the residuals RF = 0.037 and RwF = 0.034 III contains two triosmium groupings linked by a quadruply bridging sulfido ligand and two metal-metal bonds. The quadruply bridging sulfido ligand has a highly distorted tetrahedral geometry with Os-S-Os bond angles ranging from 72.5 (1)° to 149.4 (2)°. III also contains a triply bridging sulfido ligand two bridging hydride ligands, and 17 linear terminal carbonyl ligands. For IV: space group P21/n, a = 11.124 (3) Å, b = 14.090 (5) Å, c = 18.694 (7) Å, b = 92.00 (3)°, V = 2928 (3) Å3, Z = 4, ρcalcd = 3.82 g/cm3. The structure was solved by direct methods (MULTAN) and refined (2515 reflections, F2 ≥ 3.0σ(F2)) to final values of the residuals RF = 0.054 and RwF = 0.058. The structure of IV consists of a rhombus of four osmium atoms bridged on opposite sides by quadruply bridging and triply bridging sulfido ligands. Two adjacent edges of the rhombus contain bridging Os(CO)4 groups. The other two edges contain bridging hydride ligands. When exposed to UV radiation at room temperature, I undergoes facile homolysis of the carbon-sulfur bond and yields dibenzyl, compound III and the new cluster H2Os6(CO)184-S)(μ 3-S), V. For V: space group P1, a = 9.022 (2) Å, b = 11.986 (4) Å, c = 14.370 (3) Å, α = 89.94 (2)° β = 78.23 (2)°, γ = 83.39 (3)°, V = 1511 (1) Å3, Z = 2, ρcalcd = 3.76 g/cm3. The structure was solved by the heavy-atom method and refined (3407 reflections, F2 ≥ 3.0σ(F2)) to final values of the residuals RF = 0.044 and RwF = 0.044. Compound V is structurally similar to III. It contains two groups of three osmium atoms which are linked by a quadruply bridging sulfido ligand and one metal-metal bond which also contains a symmetrical bridging carbonyl ligand. The quadruply bridging sulfido ligand contains a highly distorted tetahedral geometry, Os-S-Os angles range from 74.7 (1)° to 144.5 (2)°. In addition, there is a triply bridging sulfido ligand, two bridging hydride ligands, and 17 linear terminal carbonyl ligands. V can be converted into III both by thermolytic (68°C) and photolytic decarbonylation.

Original languageEnglish
Pages (from-to)996-1005
Number of pages10
JournalOrganometallics
Volume2
Issue number8
Publication statusPublished - 1983

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Osmium
osmium
Sulfur
Isomers
cleavage
sulfur
Carbon
isomers
Ligands
ligands
carbon
synthesis
Hydrides
hydrides
Metals
Atoms
metals
atoms
Geometry
thermal degradation

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

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@article{3407861df05f47f28428a4883d8413f1,
title = "Cleavage of carbon-sulfur bonds in thiolato ligands in osmium carbonyl cluster compounds. The synthesis and structural characterization of H2Os6(CO)18(μ4-S)(μ 3-S) and two isomers of H2Os6(CO)17(μ4-S)(μ 3-S)",
abstract = "Thermal degradation of HOs3(CO)10(μ-SCH2C6H 5), I, at 150°C leads to cleavage of the carbon-sulfur bond in the phenylmethanethiolato ligand by two competing processes. By one process the cleavage is followed by the elimination of toluene and the formation of the sulfidoosmium carbonyl clusters Os3-(CO)9(μ3-S)2, Os6(CO)16(μ4-S)(μ3-S), and Os7(CO)20(μ4-S)2. The second mechanism involves homolysis of the carbon-sulfur bond and formation of dibenzyl, the red hydride-containing hexanuclear cluster H2Os6(CO)17(μ4-S)(μ 3-S), III, and its green isomer IV. Both III and IV were characterized by X-ray crystallographic methods. For III: space group C2/c, a = 20.364 (5) {\AA}, b = 9.764 (4) {\AA}, c = 32.544 (7) {\AA}, β = 114.01 (2)°, V = 5900 (6) {\AA}3, Z = 8, ρcalcd = 3.79 g/cm3. The structure was solved by direct methods (MULTAN) and refined (2456 reflections, F2 ≥ 3.0σ(F2)) to the final values of the residuals RF = 0.037 and RwF = 0.034 III contains two triosmium groupings linked by a quadruply bridging sulfido ligand and two metal-metal bonds. The quadruply bridging sulfido ligand has a highly distorted tetrahedral geometry with Os-S-Os bond angles ranging from 72.5 (1)° to 149.4 (2)°. III also contains a triply bridging sulfido ligand two bridging hydride ligands, and 17 linear terminal carbonyl ligands. For IV: space group P21/n, a = 11.124 (3) {\AA}, b = 14.090 (5) {\AA}, c = 18.694 (7) {\AA}, b = 92.00 (3)°, V = 2928 (3) {\AA}3, Z = 4, ρcalcd = 3.82 g/cm3. The structure was solved by direct methods (MULTAN) and refined (2515 reflections, F2 ≥ 3.0σ(F2)) to final values of the residuals RF = 0.054 and RwF = 0.058. The structure of IV consists of a rhombus of four osmium atoms bridged on opposite sides by quadruply bridging and triply bridging sulfido ligands. Two adjacent edges of the rhombus contain bridging Os(CO)4 groups. The other two edges contain bridging hydride ligands. When exposed to UV radiation at room temperature, I undergoes facile homolysis of the carbon-sulfur bond and yields dibenzyl, compound III and the new cluster H2Os6(CO)18(μ4-S)(μ 3-S), V. For V: space group P1, a = 9.022 (2) {\AA}, b = 11.986 (4) {\AA}, c = 14.370 (3) {\AA}, α = 89.94 (2)° β = 78.23 (2)°, γ = 83.39 (3)°, V = 1511 (1) {\AA}3, Z = 2, ρcalcd = 3.76 g/cm3. The structure was solved by the heavy-atom method and refined (3407 reflections, F2 ≥ 3.0σ(F2)) to final values of the residuals RF = 0.044 and RwF = 0.044. Compound V is structurally similar to III. It contains two groups of three osmium atoms which are linked by a quadruply bridging sulfido ligand and one metal-metal bond which also contains a symmetrical bridging carbonyl ligand. The quadruply bridging sulfido ligand contains a highly distorted tetahedral geometry, Os-S-Os angles range from 74.7 (1)° to 144.5 (2)°. In addition, there is a triply bridging sulfido ligand, two bridging hydride ligands, and 17 linear terminal carbonyl ligands. V can be converted into III both by thermolytic (68°C) and photolytic decarbonylation.",
author = "Adams, {Richard D.} and Horv{\'a}th, {Istv{\'a}n T.} and Pradeep Mathur and Segm{\"u}ller, {Brigitte E.}",
year = "1983",
language = "English",
volume = "2",
pages = "996--1005",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "8",

}

TY - JOUR

T1 - Cleavage of carbon-sulfur bonds in thiolato ligands in osmium carbonyl cluster compounds. The synthesis and structural characterization of H2Os6(CO)18(μ4-S)(μ 3-S) and two isomers of H2Os6(CO)17(μ4-S)(μ 3-S)

AU - Adams, Richard D.

AU - Horváth, István T.

AU - Mathur, Pradeep

AU - Segmüller, Brigitte E.

PY - 1983

Y1 - 1983

N2 - Thermal degradation of HOs3(CO)10(μ-SCH2C6H 5), I, at 150°C leads to cleavage of the carbon-sulfur bond in the phenylmethanethiolato ligand by two competing processes. By one process the cleavage is followed by the elimination of toluene and the formation of the sulfidoosmium carbonyl clusters Os3-(CO)9(μ3-S)2, Os6(CO)16(μ4-S)(μ3-S), and Os7(CO)20(μ4-S)2. The second mechanism involves homolysis of the carbon-sulfur bond and formation of dibenzyl, the red hydride-containing hexanuclear cluster H2Os6(CO)17(μ4-S)(μ 3-S), III, and its green isomer IV. Both III and IV were characterized by X-ray crystallographic methods. For III: space group C2/c, a = 20.364 (5) Å, b = 9.764 (4) Å, c = 32.544 (7) Å, β = 114.01 (2)°, V = 5900 (6) Å3, Z = 8, ρcalcd = 3.79 g/cm3. The structure was solved by direct methods (MULTAN) and refined (2456 reflections, F2 ≥ 3.0σ(F2)) to the final values of the residuals RF = 0.037 and RwF = 0.034 III contains two triosmium groupings linked by a quadruply bridging sulfido ligand and two metal-metal bonds. The quadruply bridging sulfido ligand has a highly distorted tetrahedral geometry with Os-S-Os bond angles ranging from 72.5 (1)° to 149.4 (2)°. III also contains a triply bridging sulfido ligand two bridging hydride ligands, and 17 linear terminal carbonyl ligands. For IV: space group P21/n, a = 11.124 (3) Å, b = 14.090 (5) Å, c = 18.694 (7) Å, b = 92.00 (3)°, V = 2928 (3) Å3, Z = 4, ρcalcd = 3.82 g/cm3. The structure was solved by direct methods (MULTAN) and refined (2515 reflections, F2 ≥ 3.0σ(F2)) to final values of the residuals RF = 0.054 and RwF = 0.058. The structure of IV consists of a rhombus of four osmium atoms bridged on opposite sides by quadruply bridging and triply bridging sulfido ligands. Two adjacent edges of the rhombus contain bridging Os(CO)4 groups. The other two edges contain bridging hydride ligands. When exposed to UV radiation at room temperature, I undergoes facile homolysis of the carbon-sulfur bond and yields dibenzyl, compound III and the new cluster H2Os6(CO)18(μ4-S)(μ 3-S), V. For V: space group P1, a = 9.022 (2) Å, b = 11.986 (4) Å, c = 14.370 (3) Å, α = 89.94 (2)° β = 78.23 (2)°, γ = 83.39 (3)°, V = 1511 (1) Å3, Z = 2, ρcalcd = 3.76 g/cm3. The structure was solved by the heavy-atom method and refined (3407 reflections, F2 ≥ 3.0σ(F2)) to final values of the residuals RF = 0.044 and RwF = 0.044. Compound V is structurally similar to III. It contains two groups of three osmium atoms which are linked by a quadruply bridging sulfido ligand and one metal-metal bond which also contains a symmetrical bridging carbonyl ligand. The quadruply bridging sulfido ligand contains a highly distorted tetahedral geometry, Os-S-Os angles range from 74.7 (1)° to 144.5 (2)°. In addition, there is a triply bridging sulfido ligand, two bridging hydride ligands, and 17 linear terminal carbonyl ligands. V can be converted into III both by thermolytic (68°C) and photolytic decarbonylation.

AB - Thermal degradation of HOs3(CO)10(μ-SCH2C6H 5), I, at 150°C leads to cleavage of the carbon-sulfur bond in the phenylmethanethiolato ligand by two competing processes. By one process the cleavage is followed by the elimination of toluene and the formation of the sulfidoosmium carbonyl clusters Os3-(CO)9(μ3-S)2, Os6(CO)16(μ4-S)(μ3-S), and Os7(CO)20(μ4-S)2. The second mechanism involves homolysis of the carbon-sulfur bond and formation of dibenzyl, the red hydride-containing hexanuclear cluster H2Os6(CO)17(μ4-S)(μ 3-S), III, and its green isomer IV. Both III and IV were characterized by X-ray crystallographic methods. For III: space group C2/c, a = 20.364 (5) Å, b = 9.764 (4) Å, c = 32.544 (7) Å, β = 114.01 (2)°, V = 5900 (6) Å3, Z = 8, ρcalcd = 3.79 g/cm3. The structure was solved by direct methods (MULTAN) and refined (2456 reflections, F2 ≥ 3.0σ(F2)) to the final values of the residuals RF = 0.037 and RwF = 0.034 III contains two triosmium groupings linked by a quadruply bridging sulfido ligand and two metal-metal bonds. The quadruply bridging sulfido ligand has a highly distorted tetrahedral geometry with Os-S-Os bond angles ranging from 72.5 (1)° to 149.4 (2)°. III also contains a triply bridging sulfido ligand two bridging hydride ligands, and 17 linear terminal carbonyl ligands. For IV: space group P21/n, a = 11.124 (3) Å, b = 14.090 (5) Å, c = 18.694 (7) Å, b = 92.00 (3)°, V = 2928 (3) Å3, Z = 4, ρcalcd = 3.82 g/cm3. The structure was solved by direct methods (MULTAN) and refined (2515 reflections, F2 ≥ 3.0σ(F2)) to final values of the residuals RF = 0.054 and RwF = 0.058. The structure of IV consists of a rhombus of four osmium atoms bridged on opposite sides by quadruply bridging and triply bridging sulfido ligands. Two adjacent edges of the rhombus contain bridging Os(CO)4 groups. The other two edges contain bridging hydride ligands. When exposed to UV radiation at room temperature, I undergoes facile homolysis of the carbon-sulfur bond and yields dibenzyl, compound III and the new cluster H2Os6(CO)18(μ4-S)(μ 3-S), V. For V: space group P1, a = 9.022 (2) Å, b = 11.986 (4) Å, c = 14.370 (3) Å, α = 89.94 (2)° β = 78.23 (2)°, γ = 83.39 (3)°, V = 1511 (1) Å3, Z = 2, ρcalcd = 3.76 g/cm3. The structure was solved by the heavy-atom method and refined (3407 reflections, F2 ≥ 3.0σ(F2)) to final values of the residuals RF = 0.044 and RwF = 0.044. Compound V is structurally similar to III. It contains two groups of three osmium atoms which are linked by a quadruply bridging sulfido ligand and one metal-metal bond which also contains a symmetrical bridging carbonyl ligand. The quadruply bridging sulfido ligand contains a highly distorted tetahedral geometry, Os-S-Os angles range from 74.7 (1)° to 144.5 (2)°. In addition, there is a triply bridging sulfido ligand, two bridging hydride ligands, and 17 linear terminal carbonyl ligands. V can be converted into III both by thermolytic (68°C) and photolytic decarbonylation.

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