Endohedral Anionic Nine-Atom Zintl Clusters of the Elements Tin and Lead with Lithium Counterions

Abstract

Intermetalloid clusters are considered as highly charged soluble models for intermetallic phases. While their bonding situation is not fully understood, their solubility makes them promising candidates for the fabrication of nanostructured intermetallic materials. We report on the synthesis of endohedral [TM@Tt9]4- (Tt = Sn and TM = Fe, Co, Ni, Pd; Tt = Pb and TM = Pd, Pt) clusters with Li counterions in solution. The potassium ions are replaced with lithium cations through a simple salt metathesis reaction using LiCl. The intermetalloid clusters crystallize in the known structure types known from compounds containing unfilled clusters. The new compounds are further investigated by Raman, NMR, and EPR spectroscopy.