Reaction of SiCl₂·dipp with K[Ge₉{Si(SiMe₃)₃}₃] – Synthesis and Characterization of [K(dipp)₂][Ge₉{Si(SiMe₃)₃}₃]·tol and [dipp‐H][Ge₉{Si(SiMe₃)₃}₃]·2acn [dipp = 1,3‐Bis(2,6‐Diisopropylphenyl)imidazol‐2‐ylidene]

Abstract

From solutions of K[Ge 9 {Si(SiMe 3 ) 3 } 3 ] with 1,3bis(2,6-diisopropylphenyl-)imidazol-2-ylidene (dipp) two new compounds were obtained. From toluene, single crystals of [K(dipp) 2 ][Ge 9 {Si(SiMe 3 ) 3 } 3 ]·tol (1) (tol = toluene) were isolated and the crystal structure was determined [monoclinic, P2 1 /c, a = 16.8386(3), b = 24.6597(5), c = 30.2988(6) Å, β = 101.813(2)°, V = 12314.7(4) Å 3 , Z = 4, 24192 independent reflections, R 1 = 0.046, wR 2 = 0.084]. The investigation of single crystals from acetonitrile solution * Prof. Dr. T. F. Fässler Fax: +49-89-289-13186 E-Mail: Thomas.Faessler@lrz.tu-muenchen.de [a] Lehrstuhl für Anorganische Chemie mit Schwerpunkt Neue Materialien

Eclipsed- and Staggered-[Ge18Pd3{EiPr3}6]2– (E = Si, Sn): Positional Isomerism in Deltahedral Zintl Clusters

“…The same compound, but in much lower yield, was originally synthesized by the so-called subhalide approach wherein a metastable GeBr generated at 1550 °C is reacted with LiHyp at −78 °C . The hypersilylated species have been, in turn, studied for their reactivity to add a fourth substituent, to coordinate to transition metals, to aggregate, to add cluster atoms, etc. − In addition, similar heterogeneous reactions have produced clusters that are trisubstituted with other silyl-based substituents, thus demonstrating the versatility and capabilities of the proposed synthetic approach. − …”

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]

“…[16] Such silylated clusterc ompounds are able to undergo further reactions. [25] Until recently [20] only clusters with [Si(SiMe 3 ) 3 ] + and [Si(Si-Me 3 ) 2 (SiPh 3 )] + groups have been reported. [19] Starting from the precursor phaseK 4 Ge 9 it is also possible to introduce other silyl groups to the cluster and recentlyt he introduction of R = iBu, iPr,a nd Et was realized in [Ge 9 (SiR 3 ) 3 ] À , [20] whereas [Ge 9 {Si(SiMe 3 ) 2 (SiPh 3 )} 3 ] À was found in ad imericH g + complex.…”

“…[22] More recent investigations also showedt he existence of the anion [Pd (Ge 9 [24] were obtained by reaction of [Ge 9 {Si(SiMe 3 ) 3 } 3 ] À and M(NHC)Cl (NHC = N-heterocyclic carbene;M= Cu, Ag, Au), being the first compounds combining Zintl-cluster and NHC chemistry. [25] Until recently [20] only clusters with [Si(SiMe 3 ) 3 ] + and [Si(Si-Me 3 ) 2 (SiPh 3 )] + groups have been reported. [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.…”

Chemi-Inspired Silicon Allotropes—Experimentally Accessible Si9 Cages as Proposed Building Block for 1D Polymers, 2D Sheets, Single-Walled Nanotubes, and Nanoparticles

“…To reduce possible strain within the 2D network of L1 , we introduced an additional tetrahedrally coordinated Si atom as a structural fragment, leading to ( L2 ). Silicon atoms that are covalently bonded to nine-atomic clusters are known for the higher homologue Ge, where the functionalization of Ge 9 with silicon organyls leads to [Ge 9 (TMS) 3 ] - (TMS = Si[Si(CH 3 ) 3 ] 3 ) [ 87 , 88 , 89 ], and also a crosslinking of these cluster units with different bridging atoms, for example the tetrel element Sn or the Group 12 elements Hg and Zn [ 90 , 91 , 92 ], and via organic bridges can be achieved [ 93 ].…”