2015
DOI: 10.1002/hlca.201400365
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The Aggregation Behavior of Butyllithium in Diethyl Ether in the Presence of LiBr, LiClO4, and Phenyllithium: A Deuterium‐Induced Secondary6Li‐NMR Isotope‐Effect Study

Abstract: The aggregation of BuLi (LiR) in diethyl ether (Et2O) in the presence of LiBr was studied by 6Li‐ and 13C‐NMR spectroscopy. For a 1.0 : 0.8 mixture of both species, the clusters (LiR)4, Li4R3Br, Li4R2Br2, Li4RBr3, and/or Li2RBr in the ratio 7 : 81 : 12 with Li4RBr3 and/or Li2RBr<1 were detected with the isotopic fingerprint method that is based on secondary deuterium (D)‐induced isotope shifts for δ(Li). The raising content of bromide ions causes increased shielding for δ(Li). As in the case of a 1 : 1 MeLi/Li… Show more

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Cited by 5 publications
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“…When the exchange rate is not too fast yet not slow enough to afford well separated peaks, a line shape analysis of the 13 C NMR signals of carbon nuclei near these polar groups, which are affected by deuterium-proton isotope shifts in a mixture of H2O and D2O, can help identify such cases (Takeda et al, 2014). Deuterium induced isotope effects on 6 Li chemical shifts have been recently used to elucidate the structure of aggregates formed by butyllithium in diethyl ether in the presence of bromide ions (Böhler and Günther, 2015). In this particular case, the measured isotope shifts caused by deuterated butyllithium, the observed intensity pattern and multiplicity, and the shielding effect of a bromide ion are all taken into account to arrive at the identity of the nearest neighbors to lithium in the aggregate.…”
mentioning
confidence: 99%
“…When the exchange rate is not too fast yet not slow enough to afford well separated peaks, a line shape analysis of the 13 C NMR signals of carbon nuclei near these polar groups, which are affected by deuterium-proton isotope shifts in a mixture of H2O and D2O, can help identify such cases (Takeda et al, 2014). Deuterium induced isotope effects on 6 Li chemical shifts have been recently used to elucidate the structure of aggregates formed by butyllithium in diethyl ether in the presence of bromide ions (Böhler and Günther, 2015). In this particular case, the measured isotope shifts caused by deuterated butyllithium, the observed intensity pattern and multiplicity, and the shielding effect of a bromide ion are all taken into account to arrive at the identity of the nearest neighbors to lithium in the aggregate.…”
mentioning
confidence: 99%