Reduction of K+ or Li+ in the Heterobimetallic Electride K+[LiN(SiMe3)2]e.
J Am Chem Soc
; 145(31): 17007-17012, 2023 Aug 09.
Article
em En
| MEDLINE
| ID: mdl-37478322
ABSTRACT
Given their very negative redox potential (e.g., Li+ â Li(0), -3.04 V; K+ â 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.
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Base de dados:
MEDLINE
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En
Ano de publicação:
2023
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Article