Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 17, Issue 24, Pages 6725-6730Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201100523
Keywords
alkali metals; amides; crystal structures; density functional calculations; NMR spectroscopy
Categories
Funding
- UK Engineering and Physical Science Research Council [EP/F063733/1]
- Royal Society/Wolfson Foundation
- Spanish MICINN [DELACIERVA-09-05]
- EU [FP7-2010-RG-268329]
- EPSRC [EP/F063733/1, EP/E036244/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/F063733/1, EP/E036244/1] Funding Source: researchfish
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The often studied THF solvates of the utility alkali-metal amides lithium and sodium 2,2,6,6-tetramethylpiperidide are shown to exist in the solid state as asymmetric cyclic dimers containing a central M2N2 ring and one molecule of donor per metal to give a distorted trigonal planar metal coordination. DFT studies support these structures and confirm the asymmetry in the ring. In C6D12 solution, the lithium amide displays a concentration-dependent equilibrium between a solvated and unsolvated species which have been shown by diffusion-ordered NMR spectroscopy (DOSY) to be a dimer and larger oligomer, respectively. A third species, a solvated monomer, is also present in very low concentration, as proven by spiking the NMR sample with THF. In contrast, the sodium amide displays a far simpler C6D12 solution chemistry, consistent with the solid-state dimeric arrangement but with labile THF ligands.
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