Ruthenium Decorated Tris-Silylated Germanium Zintl Clusters Featuring an Unexpected Ligand Arrangement
Year: 2025
Type: article
Abstract: The incorporation of transition metal atoms into [Ge9] clusters is a widely studied area of Zintl-cluster chemistry. Recently, it was shown that clusters comprising single transition metal atoms in the cluster surface show catalytic properties. Here, we present a synthetic approach to four new compounds comprising silylated Ge9 clusters with organometallic ruthenium complexes. [η5-Ge9Hyp3]RuCp* (1), [η1-Ge9(SitBu2H)3]RuCp(PPh3)2 (2), and [Hyp3Ge9][RuCp(PPh3)2(MeCN)] (3b) (Cp = cyclopentadienyl, Cp* = pentamethylcyclopentadienyl, Hyp = Si(SiMe3)3, Ph = C6H5, tBu = tert-butyl) were characterized by means of NMR spectroscopy and single-crystal structure determination. In the case of 2, a new isomer with an approximated C4v symmetric monocapped square antiprism of nine Ge atoms with an unexpected ligand arrangement comprising three ditertbutylsilane ligands attached to the open square was obtained. [Hyp3Ge9][RuCp(PPh3)2] (3a) was characterized via NMR spectroscopy and LIFDI mass spectrometry. Overall, we were able to show that the steric demand of the ligands Cp vs. Cp* and hypersilylchloride vs. ditertbutylsilane strongly influence the arrangement of the atoms and ligands on the cluster. In addition, the solvent also affects the cluster, as it appears that the ruthenium atom in 3a dissociates from the cluster surface upon acetonitrile coordination to form 3b. These results show that choosing the right synthetic tools and ligands makes a big difference in the outcome of the metalation reaction.
Source: Molecules
Institution: Technical University of Munich
Language: English
Subfield: Inorganic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: gold
Estimated APC paid: $3,258
Funder: Wacker
OpenAlex ID: W4408339925