Retention of the Zn−Zn bond in [Ge₉Zn−ZnGe₉]⁶⁻ and Formation of [(Ge₉Zn)−(Ge₉)−(ZnGe₉)]⁸⁻ and Polymeric 1∞ [−(Ge₉Zn)²⁻−]1

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• 作者：Kerstin Mayer ; Laura-Alice Jantke ; Prof. Dr. Stephan Schulz and Prof. Dr. Thomas F. F&auml ; ssler
• 刊名：Angewandte Chemie International Edition
• 出版年：2017
• 出版时间：February 20, 2017
• 年：2017
• 卷：56
• 期：9
• 页码：2350-2355
• 全文大小：2211K
• ISSN：1521-3773

文摘

Reactions of Zn^I₂L₂ (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{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 K₄Ge₉ in ethylenediamine yielded the linear polymeric unit lass="math-equation-construct">ge="true" class="math-equation-image">l="true" class="math-equation-mathml" style="display:none">l:math xmlns:mml="http://www.w3.org/1998/Math/MathML">lns:w="http://www.wiley.com/namespaces/wiley" xmlns:wiley="http://www.wiley.com/namespaces/wiley/wiley" xmlns:cr="urn://wiley-online-library/content/render" xmlns="http://www.w3.org/1998/Math/MathML" linethickness="0pt">1∞l:math> {[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⁻.