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Structure determination using the method of continuous variation: lithium phenolates solvated by protic and dipolar aprotic ligands.

ABSTRACT: The method of continuous variation (MCV) was used in conjunction with (6)Li NMR spectroscopy to characterize four lithium phenolates solvated by a range of solvents, including N,N,N',N'-tetramethylethylenediamine, Et2O, pyridine, protic amines, alcohols, and highly dipolar aprotic solvents. Dimers, trimers, and tetramers were observed, depending on the precise lithium phenolate-solvent combinations. Competition experiments (solvent swaps) provide insights into the relative propensities toward mixed solvation.

SUBMITTER: Tomasevich LL

PROVIDER: S-EPMC3759316 | biostudies-literature | 2013 Aug

REPOSITORIES: biostudies-literature

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Structure determination using the method of continuous variation: lithium phenolates solvated by protic and dipolar aprotic ligands.

Tomasevich Laura L LL Collum David B DB

The Journal of organic chemistry 20130715 15

The method of continuous variation (MCV) was used in conjunction with (6)Li NMR spectroscopy to characterize four lithium phenolates solvated by a range of solvents, including N,N,N',N'-tetramethylethylenediamine, Et2O, pyridine, protic amines, alcohols, and highly dipolar aprotic solvents. Dimers, trimers, and tetramers were observed, depending on the precise lithium phenolate-solvent combinations. Competition experiments (solvent swaps) provide insights into the relative propensities toward mi ...[more]

PMID: 23806055

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Project description:Choline-based electrolytes have been proposed as environmentally friendly and low-cost alternatives for secondary zinc air batteries. Choline acetate [Ch]+ [OAc]- in protic (D2 O) and aprotic (DMSO-d6 ) solvents has been studied by means of concentration-dependent 1 H NMR, viscosity, and density measurements. The viscosities have been calculated on the basis of the Jones-Dole equation and showed that the dominant contribution originates from short-range ion-solvent interactions. Site-specific association affinities were assigned from NMR chemical shift titrations. In DMSO-d6 , the hydroxyl group of choline was found to have the smallest dissociation constant followed by the methyl group of acetate. The corresponding Gibbs energies at low concentration were found to be in agreement with a solvent-separated ion pair (2SIP) configuration, whereas at concentrations above 300 mM, a solvent-shared ion pair (SIP) configuration was assigned. For [Ch]+ [OAc]- in D2 O, association effects were found to be weaker, attributed to the high dielectric constant of the solvent. On time scales on the order of 100 ms, NMR linewidth perturbations indicated a change in the local rotational dynamics of the ions, attributed to short-range cation-solvent interactions and not to solvent viscosity. At 184 mM, ∼ 40 % of the cations in DMSO-d6 and ∼ 10 % in D2 O were found to exhibit short-range interactions, as indicated by the linewidth perturbations. It was found that at about 300 mM, the ions in DMSO-d6 exhibit a transition from free to collective translational dynamics on time scales on the order of 400 ms. In DMSO-d6 , both ions were found to be almost equally solvated, whereas in D2 O solvation of acetate was stronger, as indicated by the obtained effective hydrodynamic radii. For [Ch]+ [OAc]- in DMSO-d6 , the results suggest a solvent-shared ion association with weak H-bonding interactions for concentrations between 0.3-1 M. Overall, the extent of ion association in solvents such as DMSO is not expected to significantly limit charge transport and hinder the performance of choline-based electrolytes.

Dataset Information

Structure determination using the method of continuous variation: lithium phenolates solvated by protic and dipolar aprotic ligands.

Publications

Structure determination using the method of continuous variation: lithium phenolates solvated by protic and dipolar aprotic ligands.

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