Silicon clusters with six and seven unsubstituted vertices via a two-step reaction from elemental silicon

Abstract

A synthetic shortcut to molecules that contain several unprotected silicon atoms comprising the whole range from localized to delocalized Si–Si bonds.

Extracting [Pd@Sn9]4– and [Rh@Pb9]4– Clusters from their Binary Alloys Using “Metal Scissors”

“…It is known that the deltahedral clusters possess very characteristic Raman spectra , . We recently showed that endohedrally filled clusters show in contrast to the empty clusters a shift of the characteristic Raman lines of the empty clusters but also additional signals at higher wave numbers .…”

“…It is known that the deltahedral clusters possess very characteristic Raman spectra. [20,[47][48][49][50] We recently showed that endohedrally filled clusters show in contrast to the empty clusters a shift of the characteristic Raman lines of the empty clusters but also additional signals at higher wave numbers. [51] We found that Raman spectroscopy can also be applied for the Sn containing phases to show if filled clusters are present, in contrast to powder X-ray diffraction experiments that show too many reflections to determine changes in the cell parameters.…”

[Cl@Si20H20]−: Parent Siladodecahedrane with Endohedral Chloride Ion

“…Most of the synthetically accessible molecular silicon cages, such as Fässler’s [R 2 Si 9 ] 2– anions, − Kyushin’s decasilahexa­hydrotriquinacene, Marschner’s decasilaadamantane, Scheschkewitz’s siliconoids, − or the above-mentioned silatetrahedranes and -cubanes present chemically rather innocent (bulky) organyl groups to their environments. Hydrogenated species are rare, and functionalized derivatives feature mainly low-valent, nucleophilic Si sites .…”

FLP-type nitrile activation and cyclic ether ring-opening by halo-borane nonagermanide-cluster Lewis acid–base pairs

“…Thus, by treatment of solid K 4 Ge 9 with stoichiometric amounts of an acetonitrile solution of chloro-tris(trimethylsilyl)silane the twoand three-fold silylated clusters [Ge 9 {Si(TMS) 3 } 2 ] 2À 24 and [Ge 9 {Si(TMS) 3 } 3 ] À 25 are obtained, respectively. The transfer of this method to elusive [Si 9 ] clusters in the phase K 12 Si 17 yielding [Si 9 {SiR 3 } 2 ] 2À , [Si 9 {SiR 3 } 3 ] À (R ¼ TMS, t Bu 2 H), 26,27 [Si 9 H 2 ] 2À , 28 and [Si 9 H] 3À 29,30 shows the huge potential of this synthetic protocol using polar intermetallic compounds (Zintl phases) as precursors.The addition of functional groups such as silyl fragments 24,31-35 to bare [Ge 9 ] allowed for a stabilization and…”