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Although we cannot find evidence of five-rung (pentameric) ladders in the crystallographic literature, we observed them as part of nearly statistical ensembles of 3-, 4-, 5-, and 6-rung lithium diethylamide ladders
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2 by parametric fit at very low or very high relative AB concentration. It is ironic, therefore, that the parametric fits become less effective precisely when the deviation from statistical shows the distinction is most needed
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2 by parametric fit at very low or very high relative AB concentration. It is ironic, therefore, that the parametric fits become less effective precisely when the deviation from statistical shows the distinction is most needed.
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Standard ethereal ligands have been observed coordinated to lithium ion in the slow exchange limit only rarely and only at very low temperatures. Leading references: (a)
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One can infer approximate relative solvent binding constants from the proportions of the two solvents required to achieve a 50% shift. In Figure 9c, for example, the average chemical shift at equimolar THF and DME suggests a preference for the THF-solvated dimer
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(a) One can infer approximate relative solvent binding constants from the proportions of the two solvents required to achieve a 50% shift. In Figure 9c, for example, the average chemical shift at equimolar THF and DME suggests a preference for the THF-solvated dimer.
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Our first experience with solvent swaps occurred during studies of unsolvated lithium diisopropylamide in which addition of a weakly coordinating trialkylamine caused only one of several unsolvated cyclic oligomers to migrate to the chemical shift of the disolvated dimer (ref 34b).
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2AlOAr is unsolvated at Li with stabilizing Li ⋯ H(t-Bu)agostic interactions (ref 21i)
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The temperature-dependent change in solvation with warming is inferred to be desolvation because of the substantial negative enthalpies of solvation. For related desolvations, see refs 34 and 53.
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The hindered chelating ligand, TMEDA, affords no cyclic trimers (ref 7b)
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The hindered chelating ligand, TMEDA, affords no cyclic trimers (ref 7b).
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Tetrameric ladders are suggested to be of nearly equal stability when compared with the corresponding pentamers (both U-shaped; energy in kcal/mol on a per-lithium basis at -90°C)
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Tetrameric ladders are suggested to be of nearly equal stability when compared with the corresponding pentamers (both U-shaped; energy in kcal/mol on a per-lithium basis at -90°C).
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