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Dalton Trans ; 50(39): 13671-13675, 2021 Oct 12.
Artigo em Inglês | MEDLINE | ID: mdl-34570145


The syntheses and the characterization of two 17-atom 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 16- and 18-atom Ge clusters, are investigated by single crystal X-ray diffraction and by quantum chemical calculations. The structures mark a new example on the pathway for cluster growth towards larger clusters with icosahedral symmetry. Furthermore, the [Co@Ge10]3- anion (3a) is obtained from liquid ammonia.

Angew Chem Int Ed Engl ; 58(37): 12908-12913, 2019 Sep 09.
Artigo em Inglês | MEDLINE | ID: mdl-31298780


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 "K5 Co1.2 Ge9 " and "K4 Ru3 Sn7 " 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.