Superalkali-alkalide interactions and ion pairing in low-polarity solvents
File(s)
Published version
Supplementary information
Author(s)
Type
Journal Article
Abstract
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).
Date Issued
2021-03-17
Date Acceptance
2021-02-15
Citation
Journal of the American Chemical Society, 2021, 143 (10), pp.3934-3943
ISSN
0002-7863
Publisher
American Chemical Society
Start Page
3934
End Page
3943
Journal / Book Title
Journal of the American Chemical Society
Volume
143
Issue
10
Copyright Statement
© 2021 The Authors. Published by American Chemical Society. This article is open access under a Creative Commons Attribution Licence (https://creativecommons.org/licenses/by/4.0/)
License URL
Sponsor
Commission of the European Communities
Grant Number
267281
Subjects
Science & Technology
Physical Sciences
Chemistry, Multidisciplinary
Chemistry
General Chemistry
03 Chemical Sciences
Publication Status
Published
Date Publish Online
2021-03-04