<b>The Infrared and Nuclear Magnetic Resonance Spectra of Ethyllithium</b>

Brown, Theodore L.; Dickerhoof, D.W.; Bafus, Donald A.

doi:10.1021/ja00867a008

Cited by 109 publications

(135 citation statements)

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“…Proposed mechanisms for the lithium exchange in Li À 1-(nBuLi) 3 : In Scheme 2, three exchange mechanisms which have previously been proposed for intraaggregate lithium exchange in tetramers are shown: a) exchange through an eight-membered ring, [32] b) a concerted center ± edge rotation of three of the alkyl groups, [33] and c) dissociation into dimers which subsequently recombine. [9] The concerted center ± edge rotation mechanism was first proposed to explain inversion at the carbanionic carbon site in primary alkyllithium compounds.…”

Section: Discussionmentioning

confidence: 99%

Intraaggregate Fluxional Lithium and Carbanion Exchanges in a Chiral Lithium Amide/n-Butyllithium Mixed Tetramer Directly Observed by Multinuclear NMR

1999

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Li ± 6 Li and 13 C ± 13 C EXSY experiments. The degeneracy of the complex is a consequence of two-site lithium exchanges and two-site carbanion exchanges. We suggest that these exchanges proceed through mechanisms which involve reversible reaction of the tetramer to associated dimers in which the dimeric parts may rotate. These mechanisms also explain the previously observed inversion of configuration at the carbanionic centers bonded to lithium.

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Section: Discussionmentioning

confidence: 99%

Intraaggregate Fluxional Lithium and Carbanion Exchanges in a Chiral Lithium Amide/n-Butyllithium Mixed Tetramer Directly Observed by Multinuclear NMR

1999

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“…Show FTIR scans from supernatant liquid and bulk. Figure 3 shows FTIR spectra from sol and bulk dried precipitates of a 1:1 sol of L2S:LT. Lines indicate reported IR shifts of ethylithium [56][57][58]. The large stretching vibration mode observed around 3400 cm -1 is indicative of O-H bonds, present in solvent and precursor compounds.…”

Section: Spectroscopic Analysismentioning

confidence: 97%

Solution based synthesis of mixed-phase materials in the Li2TiO3–Li4SiO4 system

Hanaor

Kolb

Gan

et al. 2015

Journal of Nuclear Materials

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Abstract:As candidate tritium breeder materials for use in the ITER helium cooled pebble bed, ceramic multiphasic compounds lying in the region of the quasi-binary lithium metatitanate-lithium orthosilicate system may exhibit mechanical and physical advantages relative to single phase materials. Here we present an organometallic solution-based synthesis procedure for the low-temperature fabrication of compounds in the Li 2 TiO 3 -Li 4 SiO 4 region and investigate phase stability and transformations through temperature varied X-ray diffraction and scanning calorimetry. Results demonstrate that the metatitanate and metasilicate phases Li 2 TiO 3 and Li 2 SiO 3 readily crystallise in nanocrystalline form at temperatures below 180°C. Lithium deficiency in the region of 5% results from Li sublimation from Li 4 SiO 4 and/or from excess Li incorporation in the metatitanate phase and brings about a stoichiometry shift and product compounds with mixed lithium orthosilicate/ metasilicate content towards the Si rich region and predominantly Li 2 TiO 3 content towards the Ti rich region. Above 1150°C the transformation of monoclinic to cubic γ-Li 2 TiO 3 disordered solid-solution occurs while the melting of silicate phases indicates a likely monotectic type system with a solidus line in the region 1050°-1100°C. Synthesis procedures involving a lithium chloride precursor are not likely to be a viable option for breeder pebble synthesis as this route was found to yield materials with a more significant Li-deficiency exhibiting the crystallisation of the Li 2 TiSiO 5 phase at intermediate compositions.

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“…The first 7 Li NMR signal was recorded in 1946, 4 while 6 Li was measured a few years later. 5 Highresolution spectra for 7 Li were then reported in 1962 6 and for 6 Li in 1976. 7 For completeness, we mention that nuclear properties of the short-lived nuclides 8 Li (I = 2, half-life 0.88 s) 8 and 9 Li (I = 3 2 , half-life 178 ms) 9 have been studied in order to test nuclear models.…”

Section: General Aspectsmentioning

confidence: 99%

“…Another unstable lithium nuclide is 11 Li (half-life 8.7 ms), with a spin of I = 3 2 . In the following discussion we use the notation 6,7 Li when discussing aspects relevant to both nuclei, and 6 Li or 7 Li otherwise. As in similar cases where different nuclides of the same element are reviewed, the chemical shifts (in ppm) are identical, scalar spin-spin coupling constants are related by the factor γ ( 7 Li)/γ ( 6 Li), and relaxation mechanisms differ.…”

Section: General Aspectsmentioning

confidence: 99%