Fluxional processes and structural characterization of μ3222-C 60 triosmium cluster complexes, Os3(CO)9-n(PMe3)n3222-C 60) (n=1, 2, 3)

Hyunjoon Song, Kwangyeol Lee, Joon T. Park, Hong Young Chang, Moon Gun Choi

Research output: Contribution to journalArticle

23 Citations (Scopus)

Abstract

The title complex, Os3(CO)6(PMe3)33222-C 60) (3), has been prepared by decarbonylation of Os3(CO)93222-C60) with three equivalents of Me3NO in the presence of excess PMe3 ligand. The solid-state structures of Os3(CO)7(PMe3)23222-C 60) (2) and 3 have been determined by single-crystal X-ray diffraction studies. Compound 2 has two inequivalent equatorial phosphine ligands on adjacent osmium atoms and compound 3, with a distorted C3 symmetry, has one equivalent equatorial phosphine ligand on each osmium center. The fluxional processes of Os3(CO)8(PMe3)(μ3222-C60) (1), 2, and 3 have been examined by variable-temperature 13C- and 31P-NMR studies. Only one isomer exists in solution and a restricted ligand rotation on each phosphine-substituted osmium center appears to occur for all three compounds, 1-3. Activation barriers for the carbonyl exchange process increase with increasing phosphine substitution, presumably, due to the steric effect of the phosphine ligands.

Original languageEnglish
Pages (from-to)49-56
Number of pages8
JournalJournal of Organometallic Chemistry
Volume599
Issue number1
Publication statusPublished - 2000 Apr 9
Externally publishedYes

Fingerprint

phosphine
phosphines
Osmium
Ligands
osmium
ligands
Osmium Compounds
X-Ray Diffraction
Isomers
Ion exchange
Substitution reactions
isomers
Chemical activation
Nuclear magnetic resonance
Single crystals
activation
substitutes
solid state
X ray diffraction
Atoms

Keywords

  • Crystal structure
  • Fluxional processes
  • Metallofullerene
  • Phosphine
  • Triosmium carbonyl cluster

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Fluxional processes and structural characterization of μ3222-C 60 triosmium cluster complexes, Os3(CO)9-n(PMe3)n3222-C 60) (n=1, 2, 3). / Song, Hyunjoon; Lee, Kwangyeol; Park, Joon T.; Chang, Hong Young; Choi, Moon Gun.

In: Journal of Organometallic Chemistry, Vol. 599, No. 1, 09.04.2000, p. 49-56.

Research output: Contribution to journalArticle

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abstract = "The title complex, Os3(CO)6(PMe3)3(μ 3-η2,η2,η2-C 60) (3), has been prepared by decarbonylation of Os3(CO)9(μ3-η2,η 2,η2-C60) with three equivalents of Me3NO in the presence of excess PMe3 ligand. The solid-state structures of Os3(CO)7(PMe3)2(μ 3-η2,η2,η2-C 60) (2) and 3 have been determined by single-crystal X-ray diffraction studies. Compound 2 has two inequivalent equatorial phosphine ligands on adjacent osmium atoms and compound 3, with a distorted C3 symmetry, has one equivalent equatorial phosphine ligand on each osmium center. The fluxional processes of Os3(CO)8(PMe3)(μ3-η 2,η2,η2-C60) (1), 2, and 3 have been examined by variable-temperature 13C- and 31P-NMR studies. Only one isomer exists in solution and a restricted ligand rotation on each phosphine-substituted osmium center appears to occur for all three compounds, 1-3. Activation barriers for the carbonyl exchange process increase with increasing phosphine substitution, presumably, due to the steric effect of the phosphine ligands.",
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AB - The title complex, Os3(CO)6(PMe3)3(μ 3-η2,η2,η2-C 60) (3), has been prepared by decarbonylation of Os3(CO)9(μ3-η2,η 2,η2-C60) with three equivalents of Me3NO in the presence of excess PMe3 ligand. The solid-state structures of Os3(CO)7(PMe3)2(μ 3-η2,η2,η2-C 60) (2) and 3 have been determined by single-crystal X-ray diffraction studies. Compound 2 has two inequivalent equatorial phosphine ligands on adjacent osmium atoms and compound 3, with a distorted C3 symmetry, has one equivalent equatorial phosphine ligand on each osmium center. The fluxional processes of Os3(CO)8(PMe3)(μ3-η 2,η2,η2-C60) (1), 2, and 3 have been examined by variable-temperature 13C- and 31P-NMR studies. Only one isomer exists in solution and a restricted ligand rotation on each phosphine-substituted osmium center appears to occur for all three compounds, 1-3. Activation barriers for the carbonyl exchange process increase with increasing phosphine substitution, presumably, due to the steric effect of the phosphine ligands.

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