Metal-induced cleavage of carbon-sulfur bonds in thiolato ligands. Thermolysis of HOs3(CO)10(μ-SC6H5) under CO pressure. The synthesis and crystal and molecular structures off Os4(CO)133-S) and Os5(CO)154-S)

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

Research output: Contribution to journalArticle

59 Citations (Scopus)

Abstract

The thermolysis of HOs3(CO)10(μ-SC6H5), I, has been studied under carbon monoxide pressures of 200 and 1800 psi at 150°C. At 200 psi, I eliminates C6H6 and forms the new compounds Os4(CO)133-S), II, and Os5(CO)154-S), III, and the known compounds Os3(CO)93-S)2, IV, and Os3(CO)12. Compounds II and III have been characterized by X-ray crystallographic methods. For II: space group P1, No. 2, a = 9.608 (2) Å, b = 15.402 (2) Å, c = 15.703 (3) Å, α = 113.29 (2)°, β = 99.04 (2)°, γ = 95.52 (2)°, V = 2077 (2) Å3, Z = 4, ρcalcd = 3.70 g/cm3. The structure was solved by the heavy-atom method. For 3998 reflections (F2 ≥ 3.0σ(F2)) RF = 0.040 and RwF = 0.046. The structure consists of a butterfly cluster of four osmium atoms with a triply bridging sulfido ligand on one triangular group of three. There are 13 linear terminal carbonyl ligands. When heated in the absence of CO, II loses 1 mol of CO and forms the Os4(CO)123-S) which contains a closed tetrahedron of four metal atoms. For III: space group Pna21, No. 33, a = 19.119 (4) Å, b = 7.724 (6) Å, c = 16.417 (4) Å, V = 2424 (3) Å3, Z = 4, ρcalcd = 3.84 g/cm3. The structure was solved by direct methods. For 1520 reflections (F2 ≥ 3.0σ(F2)) RF = 0.037 and RwF = 0.042. The structure consists of a square-pyramidal cluster of five osmium atoms with a quadruply bridging sulfido ligand spanning the square base. Each metal atom contains three linear terminal carbonyl ligands. At 1800 psi of CO pressure thermolysis of I yields C6H6, Os3(CO)93-S)2, and Os(CO)5 only. A reaction mechanism involving Os3-(CO)93-S) and Os(CO)4 intermediates is proposed and discussed.

Original languageEnglish
Pages (from-to)1301-1308
Number of pages8
JournalOrganometallics
Volume2
Issue number10
Publication statusPublished - 1983

Fingerprint

Thermolysis
Sulfur
Molecular structure
cleavage
molecular structure
sulfur
Carbon
Crystal structure
Metals
Ligands
Atoms
ligands
crystal structure
carbon
Osmium
synthesis
metals
osmium
atoms
Carbon Monoxide

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

@article{6ef108febf8c4d3f84bef0ac9239338f,
title = "Metal-induced cleavage of carbon-sulfur bonds in thiolato ligands. Thermolysis of HOs3(CO)10(μ-SC6H5) under CO pressure. The synthesis and crystal and molecular structures off Os4(CO)13(μ3-S) and Os5(CO)15(μ4-S)",
abstract = "The thermolysis of HOs3(CO)10(μ-SC6H5), I, has been studied under carbon monoxide pressures of 200 and 1800 psi at 150°C. At 200 psi, I eliminates C6H6 and forms the new compounds Os4(CO)13(μ3-S), II, and Os5(CO)15(μ4-S), III, and the known compounds Os3(CO)9(μ3-S)2, IV, and Os3(CO)12. Compounds II and III have been characterized by X-ray crystallographic methods. For II: space group P1, No. 2, a = 9.608 (2) {\AA}, b = 15.402 (2) {\AA}, c = 15.703 (3) {\AA}, α = 113.29 (2)°, β = 99.04 (2)°, γ = 95.52 (2)°, V = 2077 (2) {\AA}3, Z = 4, ρcalcd = 3.70 g/cm3. The structure was solved by the heavy-atom method. For 3998 reflections (F2 ≥ 3.0σ(F2)) RF = 0.040 and RwF = 0.046. The structure consists of a butterfly cluster of four osmium atoms with a triply bridging sulfido ligand on one triangular group of three. There are 13 linear terminal carbonyl ligands. When heated in the absence of CO, II loses 1 mol of CO and forms the Os4(CO)12(μ3-S) which contains a closed tetrahedron of four metal atoms. For III: space group Pna21, No. 33, a = 19.119 (4) {\AA}, b = 7.724 (6) {\AA}, c = 16.417 (4) {\AA}, V = 2424 (3) {\AA}3, Z = 4, ρcalcd = 3.84 g/cm3. The structure was solved by direct methods. For 1520 reflections (F2 ≥ 3.0σ(F2)) RF = 0.037 and RwF = 0.042. The structure consists of a square-pyramidal cluster of five osmium atoms with a quadruply bridging sulfido ligand spanning the square base. Each metal atom contains three linear terminal carbonyl ligands. At 1800 psi of CO pressure thermolysis of I yields C6H6, Os3(CO)9(μ3-S)2, and Os(CO)5 only. A reaction mechanism involving Os3-(CO)9(μ3-S) and Os(CO)4 intermediates is proposed and discussed.",
author = "Adams, {Richard D.} and I. Horv{\'a}th and Segm{\"u}ller, {Brigitte E.} and Yang, {Li Wu}",
year = "1983",
language = "English",
volume = "2",
pages = "1301--1308",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "10",

}

TY - JOUR

T1 - Metal-induced cleavage of carbon-sulfur bonds in thiolato ligands. Thermolysis of HOs3(CO)10(μ-SC6H5) under CO pressure. The synthesis and crystal and molecular structures off Os4(CO)13(μ3-S) and Os5(CO)15(μ4-S)

AU - Adams, Richard D.

AU - Horváth, I.

AU - Segmüller, Brigitte E.

AU - Yang, Li Wu

PY - 1983

Y1 - 1983

N2 - The thermolysis of HOs3(CO)10(μ-SC6H5), I, has been studied under carbon monoxide pressures of 200 and 1800 psi at 150°C. At 200 psi, I eliminates C6H6 and forms the new compounds Os4(CO)13(μ3-S), II, and Os5(CO)15(μ4-S), III, and the known compounds Os3(CO)9(μ3-S)2, IV, and Os3(CO)12. Compounds II and III have been characterized by X-ray crystallographic methods. For II: space group P1, No. 2, a = 9.608 (2) Å, b = 15.402 (2) Å, c = 15.703 (3) Å, α = 113.29 (2)°, β = 99.04 (2)°, γ = 95.52 (2)°, V = 2077 (2) Å3, Z = 4, ρcalcd = 3.70 g/cm3. The structure was solved by the heavy-atom method. For 3998 reflections (F2 ≥ 3.0σ(F2)) RF = 0.040 and RwF = 0.046. The structure consists of a butterfly cluster of four osmium atoms with a triply bridging sulfido ligand on one triangular group of three. There are 13 linear terminal carbonyl ligands. When heated in the absence of CO, II loses 1 mol of CO and forms the Os4(CO)12(μ3-S) which contains a closed tetrahedron of four metal atoms. For III: space group Pna21, No. 33, a = 19.119 (4) Å, b = 7.724 (6) Å, c = 16.417 (4) Å, V = 2424 (3) Å3, Z = 4, ρcalcd = 3.84 g/cm3. The structure was solved by direct methods. For 1520 reflections (F2 ≥ 3.0σ(F2)) RF = 0.037 and RwF = 0.042. The structure consists of a square-pyramidal cluster of five osmium atoms with a quadruply bridging sulfido ligand spanning the square base. Each metal atom contains three linear terminal carbonyl ligands. At 1800 psi of CO pressure thermolysis of I yields C6H6, Os3(CO)9(μ3-S)2, and Os(CO)5 only. A reaction mechanism involving Os3-(CO)9(μ3-S) and Os(CO)4 intermediates is proposed and discussed.

AB - The thermolysis of HOs3(CO)10(μ-SC6H5), I, has been studied under carbon monoxide pressures of 200 and 1800 psi at 150°C. At 200 psi, I eliminates C6H6 and forms the new compounds Os4(CO)13(μ3-S), II, and Os5(CO)15(μ4-S), III, and the known compounds Os3(CO)9(μ3-S)2, IV, and Os3(CO)12. Compounds II and III have been characterized by X-ray crystallographic methods. For II: space group P1, No. 2, a = 9.608 (2) Å, b = 15.402 (2) Å, c = 15.703 (3) Å, α = 113.29 (2)°, β = 99.04 (2)°, γ = 95.52 (2)°, V = 2077 (2) Å3, Z = 4, ρcalcd = 3.70 g/cm3. The structure was solved by the heavy-atom method. For 3998 reflections (F2 ≥ 3.0σ(F2)) RF = 0.040 and RwF = 0.046. The structure consists of a butterfly cluster of four osmium atoms with a triply bridging sulfido ligand on one triangular group of three. There are 13 linear terminal carbonyl ligands. When heated in the absence of CO, II loses 1 mol of CO and forms the Os4(CO)12(μ3-S) which contains a closed tetrahedron of four metal atoms. For III: space group Pna21, No. 33, a = 19.119 (4) Å, b = 7.724 (6) Å, c = 16.417 (4) Å, V = 2424 (3) Å3, Z = 4, ρcalcd = 3.84 g/cm3. The structure was solved by direct methods. For 1520 reflections (F2 ≥ 3.0σ(F2)) RF = 0.037 and RwF = 0.042. The structure consists of a square-pyramidal cluster of five osmium atoms with a quadruply bridging sulfido ligand spanning the square base. Each metal atom contains three linear terminal carbonyl ligands. At 1800 psi of CO pressure thermolysis of I yields C6H6, Os3(CO)9(μ3-S)2, and Os(CO)5 only. A reaction mechanism involving Os3-(CO)9(μ3-S) and Os(CO)4 intermediates is proposed and discussed.

UR - http://www.scopus.com/inward/record.url?scp=0000501285&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000501285&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0000501285

VL - 2

SP - 1301

EP - 1308

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 10

ER -