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Reduction of K+ or Li+ in the Heterobimetallic Electride K+[LiN(SiMe3)2]e-

Lookup NU author(s): Dr Nathan Davison, Dr Paul Waddell, Dr Erli Lu

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This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).


Abstract

© 2023 The Authors. Published by American Chemical Society.Given their very negative redox potential (e.g., Li+ → Li(0), −3.04 V; K+ → K(0), −2.93 V), chemical reduction of Group-1 metal cations is one of the biggest challenges in inorganic chemistry: they are widely accepted as irreducible in the synthetic chemistry regime. Their reduction usually requires harsh electrochemical conditions. Herein we suggest a new strategy: via a heterobimetallic electride intermediate and using the nonbinding “free” electron as reductant. Based on our previously reported K+[LiN(SiMe3)2]e- heterobimetallic electride, we demonstrate the reducibility of both K+ and Li+ cations. Moreover, we find that external Lewis base ligands, namely tris[2-(dimethylamino)ethyl]amine (Me6Tren) or 2,2,2-cryptand, can exert a level of reducing selectivity by preferably binding to Li+ (Me6Tren) or K+ (2,2,2-cryptand), hence pushing the electron to the other cation.


Publication metadata

Author(s): Davison N, Waddell PG, Lu E

Publication type: Article

Publication status: Published

Journal: Journal of the American Chemical Society

Year: 2023

Volume: 145

Issue: 31

Pages: 17007-17012

Print publication date: 09/08/2023

Online publication date: 21/07/2023

Acceptance date: 09/06/2023

Date deposited: 12/09/2023

ISSN (print): 0002-7863

ISSN (electronic): 1520-5126

Publisher: American Chemical Society

URL: https://doi.org/10.1021/jacs.3c06066

DOI: 10.1021/jacs.3c06066

PubMed id: 37478322


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Funding

Funder referenceFunder name
E22-3348740748
Newcastle University Academic Track (NUAcT)
Royal Society of Chemistry

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