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Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of Chalcogenidoplumbates(II or IV)
Published on: December 29, 2016
Synthesis and theoretical studies on rare three-coordinate lead complexes.
Matthew Chen1, J Robin Fulton, Peter B Hitchcock
1Department of Chemistry, University of Sussex, Falmer, Brighton, BN1 9QJ, UK.
Dalton Transactions (Cambridge, England : 2003)
|June 27, 2007
Summary
New beta-diketiminate lead halide complexes were synthesized, including a rare three-coordinate lead iodide. DFT calculations revealed a stereochemically active lone pair influencing geometry and differing from germanium and tin analogues.
Area of Science:
- Organometallic Chemistry
- Main Group Chemistry
- Coordination Chemistry
Background:
- Beta-diketiminate ligands are versatile in stabilizing metal complexes.
- Lead halide complexes are of interest due to lead's unique electronic properties.
- Understanding the role of lone pairs in main group element geometry is crucial.
Purpose of the Study:
- Synthesize novel beta-diketiminate lead halide complexes.
- Characterize the stability and structural features of these complexes.
- Investigate the influence of the stereochemically active lone pair on geometry using DFT calculations.
Main Methods:
- Synthesis of lead chloride, bromide, and iodide complexes.
- Stability studies in solid and solution states.
- Density Functional Theory (DFT) calculations to analyze electronic structure and geometry.
Main Results:
- Successful synthesis of LPbCl (2), LPbBr (3), and LPbI (4), with (4) being a rare three-coordinate lead iodide.
- Complexes 2 and 3 exhibit moderate stability, while 4 is less stable.
- DFT calculations show a pyramidal arrangement around lead due to an active lone pair, which is more diffuse than in germanium and tin analogues.
Conclusions:
- Beta-diketiminate ligands effectively stabilize lead halide complexes.
- The stereochemically active lone pair significantly influences the geometry of lead complexes.
- Lead's lone pair exhibits distinct electronic properties compared to germanium and tin.
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