{Ge₉[Si(SiMe₃)₂(SiPh₃)]₃}⁻: Ligand Modification in Metalloid Germanium Cluster Chemistry

Abstract

The influence of the stabilizing ligand on the physical and chemical properties of a metalloid cluster compound is important for nanotechnology as metalloid clusters are ideal model compounds for metal nanoparticles. Here we present the synthesis of a differently substituted metalloid {Ge9R3}(-) cluster: {Ge9[Si(SiMe3)2(SiPh3)]3}(-) 1, which is obtained in good yield by the reaction of K4Ge9 with ClSi(SiMe3)2(SiPh3). 1 is characterized via NMR and mass spectrometry, but crystallization is hindered. However, the reaction with HgCl2 gives the neutral compound HgGe18[Si(SiMe3)2(SiPh3)]6 2, which can be crystallized and structurally characterized. The presented results are a first step for the investigation of the ligand's influence on the properties of a metalloid germanium cluster compound.

On the Reactivity of Silylated Ge9 Clusters: Synthesis and Characterization of [ZnCp*(Ge9{Si(SiMe3)3}3)], [CuPiPr3(Ge9{Si(SiMe3)3}3)], and [(CuPiPr3)4{Ge9(SiPh3)2}2]

“…The known silylated Ge 9 clusters [Ge 9 {Si(SiMe 3 ) 3 } 3 ] À [15] and [Ge 9 {Si(SiMe 3 ) 2 (SiPh 3 )} 3 ] À [21] carry both very bulky substituents. Therefore, we attempted to synthesize silylated speciesw ith sterically less demandings ilyl groups.…”

“…Therefore, we attempted to synthesize silylated speciesw ith sterically less demandings ilyl groups. [16,21] Investigation of the resulting red solutionb yE SI-MS and NMR spectroscopy shows the formation of the tris-silylated species [Ge 9 (SiPh 3 ) 3 ] À (4). [16,21] Investigation of the resulting red solutionb yE SI-MS and NMR spectroscopy shows the formation of the tris-silylated species [Ge 9 (SiPh 3 ) 3 ] À (4).…”

“…The first silylated Ge 9 cluster compound [Ge 9 {Si(SiMe 3 ) 3 } 3 ] À waso btainedi ns mall amountss tartingf rom GeBr. [21] Aside from the tris-silylated clusterc ompounds analogous mono-a nd bis-silylated derivatives can also be synthesized. [16] Such silylated clusterc ompounds are able to undergo further reactions.…”

“…The dimeric compounds [M (Ge 9 {Si(SiMe 3 ) 3 } 3 ) 2 ]( M = Zn, Cd, Hg) were obtainedb yr eaction with the corresponding MCl 2 salts in THF, [17] and reactions of coinage metal compounds lead to anionic dimeric com-plexes [M(Ge 9 {Si(SiMe 3 ) 3 } 3 ) 2 ] À (M = Cu, Ag, and Au), [18] but also monomeric clusteru nits like [(Ge 9 {Si(SiMe 3 ) 3 } 3 )Cr(CO) 5 ] À and [(Ge 9 {Si(SiMe 3 ) 3 } 3 )Cr(CO) 3 ] À are accessible by this route. [15,16,21] We expected that less bulky ligands and ligands with different electronic properties might lead to an enhanced and different reactivity, respectively.Inorder to get abetter understanding of the reactions and to improve the reactivity of these species, we studied the reactions of the tris-silylated cluster [Ge 9 {Si(SiMe 3 ) 3 } 3 ] À with organometallic compounds and the influence on the reactivity of the cluster core also by introducing different silyl groups. [21] Aside from the tris-silylated clusterc ompounds analogous mono-a nd bis-silylated derivatives can also be synthesized.…”

N-Heterocyclic Carbene Coinage Metal Complexes of the Germanium-Rich Metalloid Clusters [Ge9R3]− and [Ge9RI2]2− with R = Si(iPr)3 and RI = Si(TMS)3

“…The resulting bis- and tris-silylated cluster species [Ge 9 R 2 ] 2− (R = Si(TMS) 3 ) [14] and [Ge 9 R 3 ] − (R: various silyl groups) [15,16,17,18,19,20] are, due to their lower charge, soluble in common solvents (acetonitrile, thf, toluene). Subsequent reactions of the tris-silylated cluster [Ge 9 R 3 ] − (R: Si(TMS) 3 ) with coinage metal complexes, in most cases coinage metal phosphine complexes, commonly yield coinage metal-bridged cluster dimers, under the loss of the original ligand sphere of the transition metal [19,21,22].…”