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Article Abstract
Zintl phases are excellent precursors for nine atom [E] clusters, which are readily accessible by dissolution of AE phases (A = Na-Rb; E = Ge-Pb) in ethylenediamine (en). In contrast, the binary alkali-metal tetrel phases of composition AE are insoluble in en. Furthermore, Li cations are rarely investigated as counterions for tetrel element Zintl clusters. We report here that KE, comprising [E] polyanions (E = Ge, Sn, and Pb), which are insoluble in en, readily dissolves in en in the presence of lithium ions and the four atomic polyanions [E] are oxidized to nine-atom [E] clusters during dissolution. We isolated crystals of [Li(en)][Ge] and [Li(en)][E] (E = Sn and Pb) with exclusively Li counterions. Furthermore, the alkali-metal ion exchange of KGe with LiCl in en results also in the oxidation of [Ge] to [Ge-Ge] dimers which were isolated as partially and fully ion-exchanged salts such as K[Li(en)][Ge-Ge] and [Li(en)][Ge-Ge], respectively. NMR spectroscopic investigations of solutions of [Sn] that contain variable Li:K ratio reveal contact K/[Sn] ion pairs, while Li ions form solvent-separated ion pairs. The role of Li ions on the solubility of Zintl phases and Li assisted oxidation of Zintl ions is highlighted.
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| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC12063050 | PMC |
| http://dx.doi.org/10.1002/chem.202500592 | DOI Listing |
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