Retention of the Zn−Zn bond in [Ge 9 Zn−ZnGe 9 ] 6− and Formation of [(Ge 9 Zn)−(Ge 9 )−(ZnGe 9 )] 8− and Polymeric 1 ∞ [−(Ge 9 Zn) 2− −] 1

Reactions of Zn I 2 L 2 (where L=[HC(PPh 2 NPh)] − ) with solutions of the Zintl phase K 4 Ge 9 in liquid ammonia lead to retention of the Zn−Zn bond and formation of the anion [(η 4 ‐Ge 9 )Zn−Zn(η 4 ‐Ge 9 )] 6− , representing the first complex with a Zn−Zn unit carrying two cluster entities. The trimeric anion [(η 4 ‐Ge 9 )Zn{μ 2 (η 1 :η 1 Ge 9 )}Zn(η 4 ‐Ge 9 )] 8− forms as a side product, indicating that oxidation reactions also take place. The reaction of Zn 2 Cp* 2 (Cp*=1,2,3,4,5‐pentamethylcyclopentadienyl) with K 4 Ge 9 in ethylenediamine yielded the linear polymeric unit1∞ {[Zn[μ 2 (η 4 :η 1 Ge 9 )]} 2− 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 9 Zn] 2− and (paramagnetic) [Ge 9 Zn] 3− .