Reduction of K(+) or Li(+) in the Heterobimetallic Electride K(+)[LiN(SiMe(3))(2)]e(–)

[Image: see text] 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(SiMe(3))(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 (Me(6)Tren) or 2,2,2-cryptand, can exert a level of reducing selectivity by preferably binding to Li(+) (Me(6)Tren) or K(+) (2,2,2-cryptand), hence pushing the electron to the other cation.