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Thioether coordination to divalent selenium halide acceptors--synthesis, properties and structures
Andrew Jolleys1, William Levason, Gillian Reid
1School of Chemistry, University of Southampton, Southampton SO17 1BJ, UK.
Dalton Transactions (Cambridge, England : 2003)
|December 20, 2012
Summary
Tetravalent selenium halides (SeCl4 and SeBr4) react with thioether ligands to form various selenium(II) thioether complexes. These complexes exhibit diverse structures, including polymers and molecular compounds, with varying stability.
Area of Science:
- Inorganic Chemistry
- Organometallic Chemistry
- Coordination Chemistry
Background:
- Tetravalent selenium halides (SeCl4, SeBr4) are reactive precursors in coordination chemistry.
- Thioether ligands offer diverse coordination modes and steric properties.
- Understanding the reactivity of SeX4 with sulfur donors is crucial for synthesizing novel selenium compounds.
Purpose of the Study:
- To investigate the reactions of SeCl4 and SeBr4 with various thioether ligands.
- To characterize the resulting selenium(II) thioether complexes structurally and spectroscopically.
- To explore the influence of ligand structure on the coordination geometry and stability of the products.
Main Methods:
- Reaction of SeCl4 and SeBr4 with thioether ligands (e.g., SMe2, tht, MeS(CH2)nSMe, o-C6H4(SMe)2) in MeCN solution.
- Isolation and characterization of products using X-ray crystallography.
- Spectroscopic analysis (NMR, IR) to confirm structures.
Main Results:
- Formation of diverse Se(II) thioether complexes, including halo-bridged polymers, molecular trans-complexes, and thioether-bridged polymers.
- Crystallographic characterization of [SeX2(SMe2)] polymers, trans-[SeX2(tht)2], cis-[SeBr2{MeS(CH2)2SMe}], and [SeBr2{MeS(CH2)3SMe}].
- Observation of rare coordination modes and C-S bond coupling reactions leading to sulfonium species, particularly with o-phenylene dithioethers.
Conclusions:
- SeCl4 and SeBr4 readily react with thioether ligands to yield a variety of Se(II) complexes.
- Ligand structure significantly influences the resulting coordination geometry and product formation.
- C-S bond activation and sulfonium salt formation are notable reaction pathways, especially with chelating thioethers.
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