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 “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.

Endohedrale Cluster gelten als molekulare Modelle für intermetallische Verbindungen – eine Verbindungsklasse mit kaum verstandenen Bindungsprinzipien. Wir berichten hier über lösliche Clusteranionen mit den bisher höchsten Ladungen pro Clustereinheit. Die Cluster zeigen die große Ähnlichkeit zwischen intermetalloiden Clustern und den entsprechenden Koordinationspolyedern in intermetallischen Verbindungen auf. Während bereits viele endohedrale Zintl‐Ionen über Reaktionen in Lösung erhalten wurden, haben wir nun die Raman‐Spektroskopie als eine zuverlässige Sonde für den erstmaligen Nachweis von diskreten endohedral gefüllten Clustern in intermetallischen Phasen etabliert. Die ternären Vorläuferlegierungen der nominellen Zusammensetzungen “K5Co1.2Ge9” und “K4Ru3Sn7” zeigen charakteristische Bindungsmoden, die von Metallatomen im Zentrum polyedrischer Cluster herrühren, was zeigt, dass in diesen Legierungen gefüllte Cluster vorliegen. Außerdem berichten wir über die strukturelle Charakterisierung von [Co@Ge9]5− (1a) und [Ru@Sn9]6− (2a), die aus Lösungen der entsprechenden Legierungen erhalten wurden.

The syntheses and the characterization of two 17-atomic endohedral Ge clusters, [Co2@Ge17]6– (1a) and [Ni2@Ge17]4– (2a), are reported. The anions 1a and 2a, which close the gap between the known...

By using different transition metal containing precursors and liquid ammonia as solvent, single crystals of Sn 4 4cluster containing ammoniates were grown, and three new compounds have been characterized by single crystal structure determination. K 4 Sn 4 • 8 NH 3 (1) (P6 3 , a = 13.0370( 6) Å and c = 39.0889(11) Å) has been obtained by dissolving a precursor with the nominal composition "KRuSn 4 " in liquid ammonia, and Rb 2 Na 2 Sn 4 • 4.8 NH 3 (2) (Pc, a = 9.4005(3) Å, b = 15.3663(6) Å, c = 12.7312(6) Å, β = 94.675(3)°) from a similar solution of "Rb 9 Na 9 Co 16 Sn 24 ". 1 represents the last missing ammoniate of the A 4 Sn 4 compounds with heavier alkali metal cations. K 6 [OH] 2 [Sn 4 ] • 5 NH 3 (3) was crystallized from solutions of the binary Zintl phase K 12 Sn 17 in presence of AuPPh 3 Cl and cryptand [2.2.2] (P2 1 /c, a = 10.3655(1) Å, b = 12.7489(2) Å, c = 16.9137(3) Å, β = 103.212(2)°), and is the Sn 44cluster compound that appears to be stable in presence of the highest amount of hydroxide so far.