Effects of ligand substitution on the metal-metal bonding in triosmium carbonyl clusters. The crystal and molecular structures of Os33-S)2(CO)9 and Os33-S)2(CO)8PMe2Ph

Richard D. Adams, I. Horváth, Brigitte E. Segmüller, Li Wu Yang

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Abstract

The molecular structures of the compounds Os33-S)2(CO)9, I, and Os33-S)2(CO)8PMe2Ph, II, have been determined by single-crystal X-ray diffraction methods. For I: space group P1, a = 6.745 (2) Å, b = 9.503 (2) Å, c = 13.592 (3) Å, α = 82.42 (2)°, β = 84.58 (2)°, γ = 69.61 (2)°; V = 808.4 (4) Å3, Z = 2, ρcalcd = 3.64 g/cm3. The structure was solved by a combination of Patterson and difference Fourier techniques. Full-matrix least-squares refinement on 2137 reflections (Fo2 ≥ 3.0σ(F)2) yielded the final residuals RF = 0.032 and RwF = 0.038. The molecule contains an open triangular cluster of three metal atoms with two equivalent metal-metal bonds Os(1)-Os(2) = 2.814 (1) Å and Os(1)-Os(3) = 2.812 (1) Å. There are two inequivalent triply bridging sulfido ligands, and each metal atom has three linear terminal carbonyl ligands. For II: space group P1, a = 9.316 (2) Å, b = 11.346 (1) Å, c = 13.592 (3) Å, α = 71.65 (1)°, β = 71.63 (2)°, γ = 79.67 (1)°, V = 1164.5 (3) Å3, Z = 2, ρcalcd = 2.84 g/cm3. This structure was solved by a combination of Patterson and difference Fourier techniques. Full-matrix least-squares refinement on 2834 reflections (Fo2 ≥ 3.0σ(F)2) yielded the final residuals RF = 0.040 and RwF = 0.041. The structure of II is similar to that of I except that a PMe2Ph ligand has been substituted for an equatorially positioned carbonyl ligand on one of the exterior metal atoms of the cluster in a position trans to one of the metal-metal bonds. The two metal-metal bonds are significantly different. The one trans to the phosphine ligand is 2.856 (1) Å while the other is 2.770 (1) Å. The structures of I and II are compared with that of Os33-S)2(CO)8CS, III, which shows distortions in the metal-metal bonding that are similar to II. The cause of these distortions is attributed to a trans influence of the substituted ligand and is believed to be largely σ inductive in nature.

Original languageEnglish
Pages (from-to)144-148
Number of pages5
JournalOrganometallics
Volume2
Issue number1
Publication statusPublished - 1983

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metal-metal bonding
Carbon Monoxide
Molecular structure
Substitution reactions
molecular structure
Crystal structure
Metals
substitutes
Ligands
ligands
crystal structure
metals
phosphine
Atoms
atoms
matrices
phosphines

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

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Effects of ligand substitution on the metal-metal bonding in triosmium carbonyl clusters. The crystal and molecular structures of Os33-S)2(CO)9 and Os33-S)2(CO)8PMe2Ph. / Adams, Richard D.; Horváth, I.; Segmüller, Brigitte E.; Yang, Li Wu.

In: Organometallics, Vol. 2, No. 1, 1983, p. 144-148.

Research output: Contribution to journalArticle

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title = "Effects of ligand substitution on the metal-metal bonding in triosmium carbonyl clusters. The crystal and molecular structures of Os3(μ3-S)2(CO)9 and Os3(μ3-S)2(CO)8PMe2Ph",
abstract = "The molecular structures of the compounds Os3(μ3-S)2(CO)9, I, and Os3(μ3-S)2(CO)8PMe2Ph, II, have been determined by single-crystal X-ray diffraction methods. For I: space group P1, a = 6.745 (2) {\AA}, b = 9.503 (2) {\AA}, c = 13.592 (3) {\AA}, α = 82.42 (2)°, β = 84.58 (2)°, γ = 69.61 (2)°; V = 808.4 (4) {\AA}3, Z = 2, ρcalcd = 3.64 g/cm3. The structure was solved by a combination of Patterson and difference Fourier techniques. Full-matrix least-squares refinement on 2137 reflections (Fo2 ≥ 3.0σ(F)2) yielded the final residuals RF = 0.032 and RwF = 0.038. The molecule contains an open triangular cluster of three metal atoms with two equivalent metal-metal bonds Os(1)-Os(2) = 2.814 (1) {\AA} and Os(1)-Os(3) = 2.812 (1) {\AA}. There are two inequivalent triply bridging sulfido ligands, and each metal atom has three linear terminal carbonyl ligands. For II: space group P1, a = 9.316 (2) {\AA}, b = 11.346 (1) {\AA}, c = 13.592 (3) {\AA}, α = 71.65 (1)°, β = 71.63 (2)°, γ = 79.67 (1)°, V = 1164.5 (3) {\AA}3, Z = 2, ρcalcd = 2.84 g/cm3. This structure was solved by a combination of Patterson and difference Fourier techniques. Full-matrix least-squares refinement on 2834 reflections (Fo2 ≥ 3.0σ(F)2) yielded the final residuals RF = 0.040 and RwF = 0.041. The structure of II is similar to that of I except that a PMe2Ph ligand has been substituted for an equatorially positioned carbonyl ligand on one of the exterior metal atoms of the cluster in a position trans to one of the metal-metal bonds. The two metal-metal bonds are significantly different. The one trans to the phosphine ligand is 2.856 (1) {\AA} while the other is 2.770 (1) {\AA}. The structures of I and II are compared with that of Os3(μ3-S)2(CO)8CS, III, which shows distortions in the metal-metal bonding that are similar to II. The cause of these distortions is attributed to a trans influence of the substituted ligand and is believed to be largely σ inductive in nature.",
author = "Adams, {Richard D.} and I. Horv{\'a}th and Segm{\"u}ller, {Brigitte E.} and Yang, {Li Wu}",
year = "1983",
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T1 - Effects of ligand substitution on the metal-metal bonding in triosmium carbonyl clusters. The crystal and molecular structures of Os3(μ3-S)2(CO)9 and Os3(μ3-S)2(CO)8PMe2Ph

AU - Adams, Richard D.

AU - Horváth, I.

AU - Segmüller, Brigitte E.

AU - Yang, Li Wu

PY - 1983

Y1 - 1983

N2 - The molecular structures of the compounds Os3(μ3-S)2(CO)9, I, and Os3(μ3-S)2(CO)8PMe2Ph, II, have been determined by single-crystal X-ray diffraction methods. For I: space group P1, a = 6.745 (2) Å, b = 9.503 (2) Å, c = 13.592 (3) Å, α = 82.42 (2)°, β = 84.58 (2)°, γ = 69.61 (2)°; V = 808.4 (4) Å3, Z = 2, ρcalcd = 3.64 g/cm3. The structure was solved by a combination of Patterson and difference Fourier techniques. Full-matrix least-squares refinement on 2137 reflections (Fo2 ≥ 3.0σ(F)2) yielded the final residuals RF = 0.032 and RwF = 0.038. The molecule contains an open triangular cluster of three metal atoms with two equivalent metal-metal bonds Os(1)-Os(2) = 2.814 (1) Å and Os(1)-Os(3) = 2.812 (1) Å. There are two inequivalent triply bridging sulfido ligands, and each metal atom has three linear terminal carbonyl ligands. For II: space group P1, a = 9.316 (2) Å, b = 11.346 (1) Å, c = 13.592 (3) Å, α = 71.65 (1)°, β = 71.63 (2)°, γ = 79.67 (1)°, V = 1164.5 (3) Å3, Z = 2, ρcalcd = 2.84 g/cm3. This structure was solved by a combination of Patterson and difference Fourier techniques. Full-matrix least-squares refinement on 2834 reflections (Fo2 ≥ 3.0σ(F)2) yielded the final residuals RF = 0.040 and RwF = 0.041. The structure of II is similar to that of I except that a PMe2Ph ligand has been substituted for an equatorially positioned carbonyl ligand on one of the exterior metal atoms of the cluster in a position trans to one of the metal-metal bonds. The two metal-metal bonds are significantly different. The one trans to the phosphine ligand is 2.856 (1) Å while the other is 2.770 (1) Å. The structures of I and II are compared with that of Os3(μ3-S)2(CO)8CS, III, which shows distortions in the metal-metal bonding that are similar to II. The cause of these distortions is attributed to a trans influence of the substituted ligand and is believed to be largely σ inductive in nature.

AB - The molecular structures of the compounds Os3(μ3-S)2(CO)9, I, and Os3(μ3-S)2(CO)8PMe2Ph, II, have been determined by single-crystal X-ray diffraction methods. For I: space group P1, a = 6.745 (2) Å, b = 9.503 (2) Å, c = 13.592 (3) Å, α = 82.42 (2)°, β = 84.58 (2)°, γ = 69.61 (2)°; V = 808.4 (4) Å3, Z = 2, ρcalcd = 3.64 g/cm3. The structure was solved by a combination of Patterson and difference Fourier techniques. Full-matrix least-squares refinement on 2137 reflections (Fo2 ≥ 3.0σ(F)2) yielded the final residuals RF = 0.032 and RwF = 0.038. The molecule contains an open triangular cluster of three metal atoms with two equivalent metal-metal bonds Os(1)-Os(2) = 2.814 (1) Å and Os(1)-Os(3) = 2.812 (1) Å. There are two inequivalent triply bridging sulfido ligands, and each metal atom has three linear terminal carbonyl ligands. For II: space group P1, a = 9.316 (2) Å, b = 11.346 (1) Å, c = 13.592 (3) Å, α = 71.65 (1)°, β = 71.63 (2)°, γ = 79.67 (1)°, V = 1164.5 (3) Å3, Z = 2, ρcalcd = 2.84 g/cm3. This structure was solved by a combination of Patterson and difference Fourier techniques. Full-matrix least-squares refinement on 2834 reflections (Fo2 ≥ 3.0σ(F)2) yielded the final residuals RF = 0.040 and RwF = 0.041. The structure of II is similar to that of I except that a PMe2Ph ligand has been substituted for an equatorially positioned carbonyl ligand on one of the exterior metal atoms of the cluster in a position trans to one of the metal-metal bonds. The two metal-metal bonds are significantly different. The one trans to the phosphine ligand is 2.856 (1) Å while the other is 2.770 (1) Å. The structures of I and II are compared with that of Os3(μ3-S)2(CO)8CS, III, which shows distortions in the metal-metal bonding that are similar to II. The cause of these distortions is attributed to a trans influence of the substituted ligand and is believed to be largely σ inductive in nature.

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