Intermetalloid clusters: The retention of the Zn-Zn bond in [Ge9Zn-ZnGe9]6– and formation of [(Ge9Zn)-(Ge9)-(ZnGe9)]8– as well as polymeric 1∞[-(Ge9Zn)2–-]1

Reactions of ZnI2L2 (where L=[HC(PPh2NPh)]) with solutions of the Zintl phase K4Ge9 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{μ211Ge9)}Zn(η4‐Ge9)]8− forms as a side product, indicating that oxidation reactions also take place. The reaction of Zn2Cp*2 (Cp*=1,2,3,4,5‐pentamethylcyclopentadienyl) with K4Ge9 in ethylenediamine yielded the linear polymeric unit {[Zn[μ241Ge9)]}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‐[Ge9Zn]2− and (paramagnetic) [Ge9Zn]3−.



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