文摘
Reactions of Znp>Ip>2L2 (where L=[HC(PPh2NPh)]p>−p>) with solutions of the Zintl phase K4Ge9 in liquid ammonia lead to retention of the Zn−Zn bond and formation of the anion [(ηp>4p>-Ge9)Zn−Zn(ηp>4p>-Ge9)]p>6−p>, representing the first complex with a Zn−Zn unit carrying two cluster entities. The trimeric anion [(ηp>4p>-Ge9)Zn{μ2(ηp>1p>:ηp>1p>Ge9)}Zn(ηp>4p>-Ge9)]p>8−p> 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 pan data-equation-construct="true" class="math-equation-construct">pan data-equation-image="true" class="math-equation-image">pan>pan data-equation-mathml="true" class="math-equation-mathml" style="display:none">p://www.w3.org/1998/Math/MathML">p://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">pace width="2.84526pt">pace>1pace width="2.84526pt">pace>∞pan>pan> {[Zn[μ2(ηp>4p>:ηp>1p>Ge9)]}p>2−p> 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)]p>+p> 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]p>2−p> and (paramagnetic) [Ge9Zn]p>3−p>.
