An Organosilicon Cluster with an Octasilacuneane Core: A Missing Silicon Cage Motif

Abstract

Cagey silicon: A silicon cluster, consisting of sixteen silicon atoms and composed of an octasilacuneane core (red, see picture) fused with cyclotetrasilanes (orange), was synthesized by reductive tetramerization of tetrachlorocyclotetrasilane. Analytical and theoretical studies reveal the unique structural and electronic features of this organosilicon cluster.

A heavy analogue of the smallest bridgehead alkene stabilized by a base

“…The facile isomerization between compound 1 and its isomer Si 4 BBY 1 0 was confirmed both experimentally and theoretically. Synthesis and reactions of Si 4 BBE 1 in this study can be regarded also as an example of contraction and expansion of unsaturated molecular silicon clusters [37][38][39][40][41] (termed siliconoids by Scheschkewitz and colleagues 37 ), which have received much attention as possible intermediates of vapour deposition of elemental silicon 42,43 . Transformation via elimination of silylene and/or skeletal isomerization may be a fascinating growth route of well-defined silicon clusters showing unique functions.…”

Two Pentasilahousanes Fused Together

“…We have recently reported the synthesis of cyclotetrasilane‐fused octasilacuneane IV 12 and cyclopentasilane‐fused hexasilabenzvalene V 13 by the reduction of 1,1,2,2‐tetrachlorocyclotetrasilane and 1,1,2,2‐tetrachlorocyclopentasilane, respectively. Compounds IV and V are the first examples of octasilacuneane and hexasilabenzvalene derivatives, respectively.…”

“…The synthetic route to 1 is outlined in Scheme . The Wurtz‐type coupling of dichlorodisilane 2 12 with sodium in THF gave a mixture of cyclotetrasilanes 3 a and 3 b 14. The head‐to‐tail adduct 3 a was isolated in 13 % yield after washing with ethanol and purification by column chromatography on silica gel.…”

Erweiterung ungesättigter Siliciumcluster mit atomarer Genauigkeit

“…Die Funktionalisierung des gesättigten Si 4 -Kerns zu isolierbaren Te trasilatetrahedraniden K + [R 3 Si 4 À ] 7a,b wurde mit KC 8 erreicht. [18] Weitere Beispiele fürisolierbare Silicoide wurden von Iwamoto [19] (9,11)u nd Kyushin [20] (10) vorgestellt. [18] Weitere Beispiele fürisolierbare Silicoide wurden von Iwamoto [19] (9,11)u nd Kyushin [20] (10) vorgestellt.…”