[Ru(Bi8)2]6+ – A Cluster in a Highly Disordered Crystal ­Structure is the Key to the Understanding of the Coordination Chemistry of Bismuth Polycations12. Issue 14 (20th September 2013)

• Record Type: Journal Article
• Authors: Groh, Matthias F.; Isaeva, Anna; Frey, Christoph; Ruck, Michael
• Is Part Of: Zeitschrift für anorganische und allgemeine Chemie. Volume 639:Issue 14(2013)
• Page Start: 2401
• Page End: 2405
• Publication Date: 2013-09-20
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry -- Periodicals; 540
• DOI: 10.1002/zaac.201300377
• Languages: English
• ISSNs: 0044-2313

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p> Black platelets of Bi<sub>39.67(7)</sub>Ru<sub>2</sub>Br<sub>35.0(2)</sub> were crystallized from a melt of Bi, BiBr<sub>3</sub>, and Ru. In the tetragonal crystal structure [<italic>P</italic>4/<italic>mbm</italic>, <italic>a</italic> = 1311.92(6) pm, <italic>c</italic> = 3018.2(4) pm at 155(5) K], cluster cations [(Bi<sub>8</sub><sup>2+</sup>)Ru<sup>2+</sup>(Bi<sub>8</sub><sup>2+</sup>)] are embedded in a matrix of disordered bromido‐bismuthate(III) groups. A thorough analysis of the disorder in the anionic part enabled the unambiguous assignment of the cluster charge. The η<sup>4</sup>‐coordination of the two Bi<sub>8</sub><sup>2+</sup> square antiprisms to the Ru<sup>II</sup> atom in the sandwich complex resembles the bonding of Bi<sub>5</sub><sup>+</sup> and Bi<sub>8</sub><sup>2+</sup> in the clusters [(Bi<sub>5</sub><sup>+</sup>)Ru<sup>+</sup>(Bi<sub>4</sub>Br<sub>4</sub>)Ru<sup>+</sup>(Bi<sub>5</sub><sup>+</sup>)] and [(Bi<sub>8</sub><sup>2+</sup>)Ru<sup>+</sup>(Bi<sub>4</sub>Br<sub>4</sub>)Ru<sup>+</sup>(Bi<sub>5</sub><sup>+</sup>)] as well as of Bi<sub>4</sub><sup>2–</sup> in <tex-math notation="tex"><![CDATA[$\rm^{1}_{\infty}$]]></tex-math><inline-graphic xlink:href="ark:/27927/pgg4t8k1k7j" mimetype="image" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" />[(Bi<sub>4</sub><sup>2–</sup>)Ru<sup>+</sup>(Bi<sub>4</sub>Br<sub>4</sub>)Ru<sup>+</sup>]. By combining crystal chemical considerations for all mentioned compounds and using quantum chemical calculations, a common bonding scheme for the coordination compounds of bismuth polycations and polyanions was established. The η<sup>4</sup>‐coordinating bismuth polycations and polyanions act as six electron donors, comparable to <italic>nido</italic>‐carborane ligands, Zintl anions <italic>E</italic><sub>9</sub><sup>4–</sup> and <italic>E</italic><sub>5</sub><sup>6–</sup> (<italic>E</italic> = Si to Pb), cyclopentadienyl ligands, or the cyclobutadiene dianion. The electron count for the transition metal is 18 in all finite clusters.</p> </abstract>