title: Retention of the Zn-Zn bond in [Ge9Zn-ZnGe9]6-and Formation of [(Ge9Zn)-(Ge9)-(ZnGe9)]8-and Polymeric 1∞ [-(Ge9Zn)2--]1.
abstract: Reactions of ZnI2L2(where L=[HC(PPh2NPh)]-) with solutions of the Zintl phase K4Ge9in 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:η1Ge9)}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 K4Ge9in ethylenediamine yielded the linear polymeric unit 1∞ {[Zn[μ2(η4:η1Ge9)]}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-.
authors.affiliation: Department Chemie, Technische Universität München, Lichtenbergstraße 4, 85747, Garching, Germany.
authors.forename: Kerstin
authors.initials: K
authors.lastname: Mayer
authors.affiliation: Department Chemie, Technische Universität München, Lichtenbergstraße 4, 85747, Garching, Germany.
authors.forename: Laura-Alice
authors.initials: LA
authors.lastname: Jantke
authors.affiliation: Fakultät für Chemie und Center for Nanointegration Duisburg-Essen (CENIDE), Universität Duisburg-Essen, Universitätsstraße 5-7, 45141, Essen, Germany.
authors.forename: Stephan
authors.identifier: 0000-0003-2896-4488
authors.initials: S
authors.lastname: Schulz
authors.affiliation: Department Chemie, Technische Universität München, Lichtenbergstraße 4, 85747, Garching, Germany.
authors.forename: Thomas F
authors.identifier: 0000-0001-9460-8882
authors.initials: TF
authors.lastname: Fässler
keywords: Zintl clusters; germanium; heteroatomic clusters; inorganic polymers; zinc