Bisvinylated [R–Ge9–Ge9–R]4– Cluster Dimers12. Issue 6 (23rd April 2015)

• Record Type: Journal Article
• Authors: Benda, Christian B.; He, Haiyan; Klein, Wilhelm; Somer, Mehmet; Fässler, Thomas F.
• Is Part Of: Zeitschrift für anorganische und allgemeine Chemie. Volume 641:Issue 6(2015)
• Page Start: 1080
• Page End: 1086
• Publication Date: 2015-04-23
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry -- Periodicals; 540
• DOI: 10.1002/zaac.201500131
• Languages: English
• ISSNs: 0044-2313

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The syntheses, crystal structures, and NMR and Raman spectroscopic characterization of two compounds with a new member of the organically functionalized dimeric Ge<sub>9</sub>–Ge<sub>9</sub> polyanion [<italic>R</italic>–Ge<sub>9</sub>–Ge<sub>9</sub>–<italic>R</italic>]<sup>4–</sup> with <italic>R</italic> = CH=CH<sub>2</sub> are presented. [K([2.2.2]crypt)]<sub>4</sub>[(CH<sub>2</sub>=CH)–Ge<sub>9</sub>–Ge<sub>9</sub>–(CH=CH<sub>2</sub>)]<bold>·</bold>1.76 en (<bold>1</bold>) was synthesized either at elevated temperature by the reaction of K<sub>4</sub>Ge<sub>9</sub> and bis(trimethylsilyl)acetylene in ethylenediamine or at ambient temperature in the presence of Pt(PPh<sub>3</sub>)<sub>4</sub>. [K(<xref ref-type="link" rid="bib18">18</xref>crown‐6)]<sub>4</sub>[(CH<sub>2</sub>=CH)–Ge<sub>9</sub>–Ge<sub>9</sub>–(CH=CH<sub>2</sub>)]<bold>·</bold>4 en (<bold>2</bold>) was obtained from the prefabricated monomeric bisvinylated Ge<sub>9</sub> cluster [Ge<sub>9</sub>(CH=CH<sub>2</sub>)<sub>2</sub>]<sup>2–</sup> and an ethylenediamine solution of the intermetallic compound K<sub>4.79</sub>Co<sub>0.79</sub>Sn<sub>9</sub>. The reductive cleavage of one or two vinyl groups from [Ge<sub>9</sub>(CH=CH<sub>2</sub>)<sub>2</sub>]<sup>2–</sup> – a prerequisite for the latter reaction – could be shown by reacting a solution of the divinylated [Ge<sub>9</sub>(CH=CH<sub>2</sub>)<sub>2</sub>]<sup>2–</sup> anion in liquid ammonia with elemental potassium, which resulted in the formation of the ligand‐free Ge<sub>9</sub><sup>4–</sup> cluster in the new compound [K<sub>5</sub>(OH)]Ge<sub>9</sub>(NH<sub>3</sub>)<sub>11</sub> (<bold>3</bold>).</p> </abstract>