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

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.