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Metallocages for Metal Anions: Highly Charged Co@Ge95- and Ru@Sn96- Clusters Featuring Spherically Encapsulated Co- and Ru2- Anions.

08:00 EDT 12th July 2019 | BioPortfolio

Summary of "Metallocages for Metal Anions: Highly Charged Co@Ge95- and Ru@Sn96- Clusters Featuring Spherically Encapsulated Co- and Ru2- Anions."

Endohedral clusters count as molecular models for intermetallic compounds - a class of compounds in which bonding principles are scarcely understood. Here we report on soluble cluster anions with the highest charges on a single cluster known so far. The clusters reflect the close analogy between intermetalloid clusters and corresponding coordination polyhedra in intermetallic compounds. While many endohedral Zintl ions have previously been obtained via solution based reactions, we now established Raman spectroscopy as a reliable probe to assign for the first time the presence of discrete, endohedrally filled clusters in intermetallic phases. The ternary precursor alloys with nominal compositions "K5Co1.2Ge9" and "K4Ru3Sn7" exhibit characteristic bonding modes originating from metal atoms in the center of polyhedral clusters, thus revealing that filled clusters are present in these alloys. We report also on the structural characterization of [Co@Ge9]5- (1a) and [Ru@Sn9]6- (2a) obtained from solutions of the respective alloys. Quantum-chemical calculations are in agreement with the formulation of (Co1-)@[Ge9]4- and (Ru2-)@[Sn9]4-, and thus, the latter anion is a very rare example comprising a Ru(-II) species.

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Name: Angewandte Chemie (International ed. in English)
ISSN: 1521-3773
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