Si8(SitBu3)6: A Hitherto Unknown Cluster Structure in Silicon Chemistry

Fischer, Gerd; Hüch, Volker; Mayer, Péter; Vasisht, Sham Kumar; Veith, Michael; Wibeŕg, Nils

doi:10.1002/anie.200501289

Cited by 89 publications

(60 citation statements)

References 22 publications

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“…51 A third example of a silicon cluster with unsubstituted vertices had been reported by Wiberg et al who reduced a pentaiodo cyclotetrasilane affording a Si 8 R 6 derivative with two hemispheroidally coordinated silicon atoms. 52 Very recently, the reaction of 10 with chlorophosphanes has been reported to cleanly afford the corresponding yellow to orange phosphine disilenes 34a34d in good isolated yields (Scheme 13). 53 Interestingly, as shown by the preparation of the palladium complexes 35a and 35b, the coordination of a [Pd(PCy 3 ) 2 ] fragment occurs to the Si=Si bond rather than to 53 the pending phosphino group.…”

Section: ç Reactions With Main Group Element Halidesmentioning

confidence: 99%

The Versatile Chemistry of Disilenides: Disila Analogues of Vinyl Anions as Synthons in Low-valent Silicon Chemistry

Scheschkewitz

2010

Chemistry Letters

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Since the first isolation of a disila analog to vinyl anion synthons, namely lithium disilenide Tip 2 Si=Si(Tip)Li (Tip: 2,4,6-triisopropylphenyl), the number of available disilenides and their synthetic applications have rapidly expanded. Derivatives with aryl, silyl, alkyl, and hydrogen substituents have been reported and even one cyclic derivative is available. Disilenides can be used to introduce the Si=Si unit to a variety of organic and inorganic substrates. Depending on whether products feature sufficiently reactive residual functionality, the Si=Si bond is either retained or undergoes further (so far intramolecular) transformations. Heteroatom-substituted disilenes are easily accessible via disilenides. Using Tip 2 Si=Si(Tip)Li as a starting material, for instance, a variety of otherwise inaccessible compounds can be prepared: conjugated systems with more than one Si=Si unit, © 1 -transition-metal complexes, functional homo-and heteronuclear silacycles, and molecular silicon clusters with substituent-free vertices. In this review article, an account on the chemistry of disilenides is given.

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Section: ç Reactions With Main Group Element Halidesmentioning

confidence: 99%

The Versatile Chemistry of Disilenides: Disila Analogues of Vinyl Anions as Synthons in Low-valent Silicon Chemistry

Scheschkewitz

2010

Chemistry Letters

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“…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.…”

Section: Discussionmentioning

confidence: 96%

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

2014

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Bicyclo[1.1.0]but-1(2)-ene (BBE), one of the smallest bridgehead alkenes and C 4 H 4 isomers, exists theoretically as a reactive intermediate, but has not been observed experimentally. Here we successfully synthesize the silicon analogue of BBE, tetrasilabicyclo[1.1.0]but-1(2)-ene (Si 4 BBE), in a base-stabilized form. The results of X-ray diffraction analysis and theoretical study indicate that Si 4 BBE predominantly exists as a zwitterionic structure involving a tetrasilahomocyclopropenylium cation and a silyl anion rather than a bicyclic structure with a localized highly strained double bond. The reaction of base-stabilized Si 4 BBE with triphenylborane affords the [2 þ 2] cycloadduct of Si 4 BBE and the dimer of an isomer of Si 4 BBE, tetrasilabicyclo[1.1.0]butan-2-ylidene (Si 4 BBY). The facile isomerization between Si 4 BBE and Si 4 BBY is supported by theoretical calculations and trapping reactions. Structure and properties of a heavy analogue of the smallest bridgehead alkene are disclosed.

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“…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.…”

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Erweiterung ungesättigter Siliciumcluster mit atomarer Genauigkeit

et al. 2019

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Kleine bis mittelgroße Cluster treten in verschiedenen Bereichen der Chemie auf,z .B.a ls aktive Spezies der heterogenen Katalyse oder als kurzlebige Zwischenprodukte bei der chemischen Gasphasenabscheidung.Die Manipulation stabiler Repräsentanten beschränkt sich meist auf die stabilisierende Ligandenperipherie und schließt die systematische Variation des eigenschaftsbestimmenden Clustergerüsts praktisch aus.Wir berichten nun über die gezielte Erweiterung eines stabilen ungesättigten Siliciumclusters von sechs auf sieben und schließlich achtG erüstatome.D ie aufeinanderfolgende Anwendung von Lithium/Naphthalin als Reduktionsmittel und Decamethylsilicocen als elektrophile Siliciumquelle führt zur Erweiterung des Kerns um genau ein Atom mit dem Potenzial zur unendlichen Wiederholung. Kleine bis mittelgroße Cluster übernehmen Schlüsselrollen in verschiedenen technologisch wichtigen Bereichen. In heterogenen Reaktionen sind Metall-und Metallverbindungscluster leistungsfähige Katalysatoren fürc hemische Tr ansformationen im industriellen Maßstab. [1] Metall-und Halbmetallcluster sind wichtige Zwischenprodukte bei der chemischen Gasphasenabscheidung dünner Schichten und Bulkmaterialien [2] sowie der Bottom-up-Synthese von Nanopartikeln. Obwohl über eine bemerkenswerte Anzahl stabiler molekularer Cluster berichtet wurde,z .B.S i 32 R 45 À , [4] (CdSe) 34 , [5] R 20 Al 77 2À

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Si₈(SitBu₃)₆: A Hitherto Unknown Cluster Structure in Silicon Chemistry

Cited by 89 publications

References 22 publications

The Versatile Chemistry of Disilenides: Disila Analogues of Vinyl Anions as Synthons in Low-valent Silicon Chemistry

The Versatile Chemistry of Disilenides: Disila Analogues of Vinyl Anions as Synthons in Low-valent Silicon Chemistry

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

Erweiterung ungesättigter Siliciumcluster mit atomarer Genauigkeit

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