4.7 Article

A hetero-alkali-metal version of the utility amide LDA: lithium-potassium diisopropylamide

Journal

DALTON TRANSACTIONS
Volume 42, Issue 10, Pages 3704-3711

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/c2dt32204h

Keywords

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Funding

  1. UK Engineering and Physical Science Research Council [EP/F063733/1]
  2. Royal Society (Wolfson research merit award)
  3. University of Strathclyde RDF Award
  4. EPSRC [EP/F063733/1] Funding Source: UKRI
  5. Engineering and Physical Sciences Research Council [EP/F063733/1] Funding Source: researchfish

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Designed to extend the synthetically important alkali-metal diisopropylamide [(NPr2)-Pr-i; DA] class of compounds, the first example of a hetero-alkali-metallic complex of DA has been prepared as a partial TMEDA solvate. Revealed by an X-ray crystallographic study, its structure exists as a discrete lithium-rich trinuclear Li2KN3 heterocycle, with TMEDA only solvating the largest of the alkali-metals, with the two-coordinate lithium atoms being close to linearity [161.9(2)degrees]. A variety of NMR spectroscopic studies, including variable temperature and DOSY NMR experiments, suggests that this new form of LDA maintains its integrity in non-polar hydrocarbon solution. This complex thus represents a rare example of a KDA molecule which is soluble in non-polar medium without the need for excessive amounts of solubilizing Lewis donor being added.

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