Metal‐Centered Zintl Ions Isolated by Direct Extraction from Endohedral Intermetallic Precursor: [Co1–x@Sn9]4– (x ≈ 0.32) and [Co2@Sn17]5–12. Issue 14 (6th October 2014)

• Record Type: Journal Article
• Authors: He, Haiyan; Klein, Wilhelm; Jantke, Laura‐Alice; Fässler, Thomas F.
• Is Part Of: Zeitschrift für anorganische und allgemeine Chemie. Volume 640:Issue 14(2014)
• Page Start: 2864
• Page End: 2870
• Publication Date: 2014-10-06
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry -- Periodicals; 540
• DOI: 10.1002/zaac.201400379
• Languages: English
• ISSNs: 0044-2313

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Two new compounds with Co‐centered Sn<sub>9</sub> clusters were obtained by the extraction directly from the intermetallic precursor K<sub>4.79</sub>Co<sub>0.79</sub>Sn<sub>9</sub> in ethylenediamine with addition of cryptand [2.2.2]. The anions [Co<sub>0.68</sub>@Sn<sub>9</sub>]<sup>4–</sup> in K[K([2.2.2]crypt)]<sub>3</sub>[Co<sub>0.68</sub>@Sn<sub>9</sub>] (<bold>1</bold>) consisting of overlaying [Co@Sn<sub>9</sub>]<sup>4–</sup> and [Sn<sub>9</sub>]<sup>4–</sup> cluster anions are connected by K atoms to form infinite <inline-formula><alternatives><tex-math notation="tex"><![CDATA[$\rm^{1}_{\infty}$]]></tex-math><inline-graphic xlink:href="ark:/27927/pgh2cqw68s7" mimetype="image" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /></alternatives></inline-formula>K[Co<sub>0.68</sub>@Sn<sub>9</sub>] chains. The anions [Co<sub>2</sub>@Sn<sub>17</sub>]<sup>5–</sup> in [K([2.2.2]crypt)]<sub>5</sub>[Co<sub>2</sub>@Sn<sub>17</sub>]<bold>·</bold>en<bold>·</bold>tol (<bold>2</bold>) are built from two [Co@Sn<sub>9</sub>] sharing one common Sn atom, with the same composition but a different conformation as in the previously reported [K([2.2.2]crypt)]<sub>5</sub>[Co<sub>2</sub>@Sn<sub>17</sub>]. Quantum chemical calculations for the different conformers of [Co<sub>2</sub>@Sn<sub>17</sub>]<sup>5–</sup> reveal that both conformers are rather close in energy and that the short intercluster Sn–Sn distance in <bold>2</bold> does not originate from attractive interactions.</p> </abstract>