CeCl3/n‐BuLi: Unraveling Imamoto's Organocerium Reagent

CeCl3(thf) reacts at low temperatures with MeLi, t‐BuLi, and n‐BuLi to isolable organocerium complexes. Solvent‐dependent extensive n‐BuLi dissociation is revealed by 7Li NMR spectroscopy, suggesting “Ce(n‐Bu)3(thf)x” or solvent‐separated ion pairs like “[Li(thf)4][Ce(n‐Bu)4(thf)y]” as the dominant...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2021-07, Vol.60 (28), p.15622-15631
Main Authors: Berger, Tassilo, Lebon, Jakob, Maichle‐Mössmer, Cäcilia, Anwander, Reiner
Format: Article
Language:English
Subjects:
7Li NMR spectroscopy
carbonyl alkylation
cerium
Dominant species
Inspection
Ion pairs
lithium
Lithium chloride
Low temperature
Magnetic resonance spectroscopy
n-butyl
NMR
NMR spectroscopy
Nuclear magnetic resonance
Reagents
Solvents
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Summary:CeCl3(thf) reacts at low temperatures with MeLi, t‐BuLi, and n‐BuLi to isolable organocerium complexes. Solvent‐dependent extensive n‐BuLi dissociation is revealed by 7Li NMR spectroscopy, suggesting “Ce(n‐Bu)3(thf)x” or solvent‐separated ion pairs like “[Li(thf)4][Ce(n‐Bu)4(thf)y]” as the dominant species of the Imamoto reagent. The stability of complexes Li3Ln(n‐Bu)6(thf)4 increases markedly with decreasing LnIII size. Closer inspection of the solution behavior of crystalline Li3Lu(n‐Bu)6(thf)4 and mixtures of LuCl3(thf)2/n‐BuLi in THF indicates occurring n‐BuLi dissociation only at molar ratios of
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202103889