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06:35
Construction and Systematical Symmetric Studies of a Series of Supramolecular Clusters with Binary or Ternary Ammonium Triphenylacetates
Published on: February 15, 2016
Solvation and structural effects on the stability of 10-X-2 ate-complexes: a computational study
K B Wiberg1, S Sklenak, W F Bailey
1Department of Chemistry, Yale University, New Haven, Connecticut 06520-8107, USA.
The Journal of Organic Chemistry
|April 25, 2000
Summary
Organolithium ate-complexes show enhanced stability with fluorine substitution. Diaryl ate-complexes are more stable than dialkyl types, with solvent coordination crucial for stabilizing these organometallic compounds.
Area of Science:
- Organometallic chemistry
- Computational chemistry
- Lithium chemistry
Background:
- Organolithium compounds are versatile reagents in organic synthesis.
- Ate-complexes are anionic species formed from organolithium reagents.
- Understanding their stability is key to controlling reactivity.
Purpose of the Study:
- To investigate the structures and energies of various 10-X-2 ate-complexes.
- To determine factors influencing the stability of these ate-complexes.
- To assess the impact of fluorine substitution on ate-complex stability.
Main Methods:
- Density functional theory (DFT) calculations using the B3LYP/6-31+2G** level of theory.
- Studied ate-complexes derived from alkyllithiums and aryllithiums with organohalides.
- Analyzed structural and energetic properties.
Main Results:
- Diaryl ate-complexes are more stable than dialkyl ate-complexes.
- Fluorine substitution significantly enhances the stability of both diaryl and dialkyl ate-complexes.
- Calculations predict perfluoro dialkyl ate-complexes to be observable.
Conclusions:
- Fluorinated organolithium ate-complexes offer increased stability.
- Lewis basic solvent coordination is vital for stabilizing ate-complexes by sequestering lithium.
- Computational findings provide a basis for experimental exploration of novel ate-complexes.
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