Details

Autor(en) / Beteiligte

• Willmes, Philipp
• Leszczyńska, Kinga
• Heider, Yannic
• Abersfelder, Kai
• Zimmer, Michael
• Huch, Volker
• Scheschkewitz, David

Titel

Isolation and Versatile Derivatization of an Unsaturated Anionic Silicon Cluster (Siliconoid)

Ist Teil von

• Angewandte Chemie (International ed.), 2016-02, Vol.55 (8), p.2907-2910

Auflage

International ed. in English

Ort / Verlag

Germany: Blackwell Publishing Ltd

Erscheinungsjahr

2016

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• The characteristic features of bulk silicon surfaces are echoed in the related partially substituted—and thus unsaturated—neutral silicon clusters (siliconoids). The incorporation of siliconoids into more‐extended frameworks is promising owing to their unique electronic features, but further developments in this regard are limited by the notable absence of functionalized siliconoid derivatives until now. Herein we report the isolation and full characterization of the lithium salt of an anionic R5Si6‐siliconoid, thus providing the missing link between silicon‐based Zintl anions and siliconoid clusters. Proof‐of‐principle for the high potential of this species for the efficient transfer of the intact unsaturated R5Si6 moiety is demonstrated by clean reactions with representative electrophiles of Groups 13, 14, and 15. Nakedness tolerated by functionaries: An unsaturated silicon cluster (siliconoid) with a negatively charged vertex efficiently transfers the intact siliconoid motif to various electrophilic substrates. Surprisingly, the “naked” silicon atoms are tolerated by functional groups, even by a carbonyl moiety, otherwise known to be extremely reactive towards low‐coordinate silicon compounds (magenta dots=Si; R=2,4,6‐triisopropylphenyl, E=electrophile).