Retention of the Zn-Zn bond in [Ge9 Zn-ZnGe9 ]6- and Formation of [(Ge9 Zn)-(Ge9 )-(ZnGe9 )]8- and Polymeric 1∞ [-(Ge9 Zn)2- -]1.

Reactions of ZnI2 L2 (where L=[HC(PPh2 NPh)]- ) with solutions of the Zintl phase K4 Ge9 in liquid ammonia lead to retention of the Zn-Zn bond and formation of the anion [(η4 -Ge9 )Zn-Zn(η4 -Ge9 )]6- , representing the first complex with a Zn-Zn unit carrying two cluster entities. The trimeric anion [(η4 -Ge9 )Zn{μ2 (η1 :η1 Ge9 )}Zn(η4 -Ge9 )]8- forms as a side product, indicating that oxidation reactions also take place. The reaction of Zn2 Cp*2 (Cp*=1,2,3,4,5-pentamethylcyclopentadienyl) with K4 Ge9 in ethylenediamine yielded the linear polymeric unit 1∞ {[Zn[μ2 (η4 :η1 Ge9 )]}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-[Ge9 Zn]2- and (paramagnetic) [Ge9 Zn]3- .