C603– versus C604– /C602– – Synthesis and Characterization of Five Salts Containing Discrete Fullerene Anions12. Issue 5 (19th February 2014)

• Record Type: Journal Article
• Authors: Boeddinghaus, M. Bele; Klein, Wilhelm; Wahl, Bernhard; Jakes, Peter; Eichel, Rüdiger‐A.; Fässler, Thomas F.
• Is Part Of: Zeitschrift für anorganische und allgemeine Chemie. Volume 640:Issue 5(2014)
• Page Start: 701
• Page End: 712
• Publication Date: 2014-02-19
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry -- Periodicals; 540
• DOI: 10.1002/zaac.201300607
• Languages: English
• ISSNs: 0044-2313

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Five new compounds, [Rb(<xref ref-type="link" rid="bib18">18</xref>crown‐6)]<sub>3</sub>[C<sub>60</sub>] (<bold>1</bold>), [Rb(<xref ref-type="link" rid="bib18">18</xref>crown‐6)]<sub>6</sub>[C<sub>60</sub>]<sub>2</sub>(C<sub>3</sub>H<sub>7</sub>NO)<sub>2</sub>(C<sub>4</sub>H<sub>8</sub>O)<sub>2</sub> (<bold>2</bold>), [Rb(benzo<xref ref-type="link" rid="bib18">18</xref>crown‐6)]<sub>6</sub>[C<sub>60</sub>]<sub>2</sub>(C<sub>2</sub>H<sub>8</sub>N<sub>2</sub>)<sub>5</sub> (<bold>3</bold>), [Cs(benzo<xref ref-type="link" rid="bib18">18</xref>crown‐6)]<sub>3</sub>C<sub>60</sub>(C<sub>2</sub>H<sub>8</sub>N<sub>2</sub>)<sub>2</sub> (<bold>4</bold>), and [Cs<sub>3</sub>(benzo<xref ref-type="link" rid="bib18">18</xref>crown‐6)<sub>5</sub>]C<sub>60</sub>(C<sub>2</sub>H<sub>8</sub>N<sub>2</sub>)<sub>(4.5+x)</sub> (<bold>5</bold>) were synthesized and characterized by single‐crystal X‐ray structure determination. All compounds contain discrete C<sub>60</sub> anions, which are ordered in <bold>1</bold>, <bold>2</bold>, and <bold>4</bold>, where direct cation‐anion contacts occur. The unit cells of <bold>1</bold> and <bold>2</bold> contain two independent fullerides, which coordinate to the rubidium atoms either of two or of four [Rb(<xref ref-type="link" rid="bib18">18</xref>crown‐6)] units. Owing to the presence of differently coordinated fullerene units in compounds <bold>1</bold> and <bold>2</bold>, a possible disproportionation of C<sub>60</sub><sup>3–</sup> into C<sub>60</sub><sup>2–</sup> and C<sub>60</sub><sup>4–</sup> anions is discussed. In <bold>3</bold> and <bold>4</bold> the C<sub>60</sub> anions are coordinated by three Rb and Cs atoms, respectively. In all compounds the average charge of the anion is –3. Magnetic data reveal a doublet spin state for <bold>3</bold>. The EPR spectra are discussed for compounds <bold>3</bold> and <bold>5</bold>. The role of a dynamic Jahn‐Teller distortion is discussed, and we report the first IR spectroscopic data of fullerene trianions, which have been obtained in solution.</p> </abstract>