Retention of the Zn&minus;Zn bond in [Ge<sub>9sub>Zn&minus;ZnGe<sub>9sub>]<sup>6&minus;sup> and Formation of [(Ge<sub>9sub>Zn)&minus;(Ge<sub>9sub>)&minus;(ZnGe<sub>9sub>)]<sup>8&minus;sup> and Polymeric 1∞ [&minus;(Ge<sub>9sub>Zn)<sup>2&minus;sup>&minus;]1

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• 作者：Kerstin Mayer ; Laura-Alice Jantke ; Prof. Dr. Stephan Schulz and Prof. Dr. Thomas F. Fä ; 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<sup>Isup><sub>2sub>L<sub>2sub> (where L=[HC(PPh<sub>2sub>NPh)]<sup>&minus;sup>) with solutions of the Zintl phase K<sub>4sub>Ge<sub>9sub> in liquid ammonia lead to retention of the Zn&minus;Zn bond and formation of the anion [(η<sup>4sup>-Ge<sub>9sub>)Zn&minus;Zn(η<sup>4sup>-Ge<sub>9sub>)]<sup>6&minus;sup>, representing the first complex with a Zn&minus;Zn unit carrying two cluster entities. The trimeric anion [(η<sup>4sup>-Ge<sub>9sub>)Zn{μ<sub>2sub>(η<sup>1sup>:η<sup>1sup>Ge<sub>9sub>)}Zn(η<sup>4sup>-Ge<sub>9sub>)]<sup>8&minus;sup> forms as a side product, indicating that oxidation reactions also take place. The reaction of Zn<sub>2sub>Cp*<sub>2sub> (Cp*=1,2,3,4,5-pentamethylcyclopentadienyl) with K<sub>4sub>Ge<sub>9sub> in ethylenediamine yielded the linear polymeric unit <span data-equation-construct="true" class="math-equation-construct"><span data-equation-image="true" class="math-equation-image">span><span data-equation-mathml="true" class="math-equation-mathml" style="display:none">s:mml="http://www.w3.org/1998/Math/MathML">s: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">space width="2.84526pt">space>1space width="2.84526pt">space>∞span>span> {[Zn[μ<sub>2sub>(η<sup>4sup>:η<sup>1sup>Ge<sub>9sub>)]}<sup>2&minus;sup> 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)]<sup>+sup> 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<sub>9sub>Zn]<sup>2&minus;sup> and (paramagnetic) [Ge<sub>9sub>Zn]<sup>3&minus;sup>.