Witzel Benedikt J L, Klein Wilhelm, Dums Jasmin V, Boyko Marina, Fässler Thomas F
Department Chemie, Technische Universität München, Lichtenbergstrasse 4, 85747, Garching, Germany.
Angew Chem Int Ed Engl. 2019 Sep 9;58(37):12908-12913. doi: 10.1002/anie.201907127. Epub 2019 Aug 21.
Endohedral clusters count as molecular models for intermetallic compounds-a class of compounds in which bonding principles are scarcely understood. Herein we report soluble cluster anions with the highest charges on a single cluster to date. The clusters reflect the close analogy between intermetalloid clusters and corresponding coordination polyhedra in intermetallic compounds. We now establish 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 "K Co Ge " and "K Ru Sn " 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@Ge ] (1a) and [Ru@Sn ] (2a) obtained from solutions of the respective alloys.
内嵌簇合物被视为金属间化合物的分子模型，金属间化合物这类化合物的键合原理几乎不为人知。在此，我们报道了迄今为止单个簇合物上电荷最高的可溶性簇阴离子。这些簇合物反映了类金属簇合物与金属间化合物中相应配位多面体之间的紧密相似性。我们现在确立拉曼光谱法作为一种可靠的探针，首次用于确定金属间相中离散的、内填充簇合物的存在。标称组成为“K Co Ge ”和“K Ru Sn ”的三元前驱体合金展现出来自多面体簇合物中心金属原子的特征键合模式，从而表明这些合金中存在填充簇合物。我们还报道了从相应合金溶液中获得的[Co@Ge ] (1a)和[Ru@Sn ] (2a)的结构表征。
