Retention of the Zn-Zn bond in [Ge Zn-ZnGe ] and Formation of [(Ge Zn)-(Ge )-(ZnGe )] and Polymeric 1∞ [-(Ge Zn) -]1.

Reactions of Zn L (where L=[HC(PPh NPh)] ) with solutions of the Zintl phase K Ge in liquid ammonia lead to retention of the Zn-Zn bond and formation of the anion [(η -Ge )Zn-Zn(η -Ge )] , representing the first complex with a Zn-Zn unit carrying two cluster entities. The trimeric anion [(η -Ge )Zn{μ (η :η Ge )}Zn(η -Ge )] forms as a side product, indicating that oxidation reactions also take place. The reaction of Zn Cp* (Cp*=1,2,3,4,5-pentamethylcyclopentadienyl) with K Ge in ethylenediamine yielded the linear polymeric unit 1∞ {[Zn[μ (η :η Ge )]} with the first head-to-tail arrangement of ten-atom closo-clusters. All anions were obtained and structurally characterized as [A(2.2.2-crypt)] salts (A=K, Rb). Copious computational analyses at a DFT-PBE0/def2-TZVPP/PCM level of theory confirm the experimental structures and support the stability of the two hypothetical ten vertex cluster fragments closo-[Ge Zn] and (paramagnetic) [Ge Zn] .