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Superalkali-alkalide interactions and ion pairing in low-polarity solvents

Riedel, R., Seel, A. G., Malko, D., Miller, D. P., Sperling, B. T., Choi, H. ORCID:, Headen, T., Zurek, E., Porch, A. ORCID:, Kucernak, A., Pyper, N. C., Edwards, P .P. and Barrett, A. G. M. 2021. Superalkali-alkalide interactions and ion pairing in low-polarity solvents. Journal of the American Chemical Society 143 (10) , pp. 3934-3943. 10.1021/jacs.1c00115

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The nature of anionic alkali metals in solution is traditionally thought to be “gaslike” and unperturbed. In contrast to this noninteracting picture, we present experimental and computational data herein that support ion pairing in alkalide solutions. Concentration dependent ionic conductivity, dielectric spectroscopy, and neutron scattering results are consistent with the presence of superalkali–alkalide ion pairs in solution, whose stability and properties have been further investigated by DFT calculations. Our temperature dependent alkali metal NMR measurements reveal that the dynamics of the alkalide species is both reversible and thermally activated suggesting a complicated exchange process for the ion paired species. The results of this study go beyond a picture of alkalides being a “gaslike” anion in solution and highlight the significance of the interaction of the alkalide with its complex countercation (superalkali).

Item Type: Article
Date Type: Publication
Status: Published
Schools: Engineering
Publisher: American Chemical Society
ISSN: 0002-7863
Date of First Compliant Deposit: 26 February 2021
Date of Acceptance: 27 January 2021
Last Modified: 09 Nov 2023 14:48

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