Anionic Siliconoids from Zintl Phases

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Journal Title
Journal ISSN
Volume Title
A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
Date
2018-12-20
Major/Subject
Mcode
Degree programme
Language
en
Pages
4
19171-19174
Series
Chemistry - A European Journal, Volume 24, issue 72
Abstract
Neutral and anionic silicon clusters (siliconoids) are regarded as important model systems for bulk silicon surfaces. For 25 years their formation from binary alkali metal silicide phases has been proposed, but experimentally never realized. Herein the silylation of a silicide, leading to the anionic siliconoids (Si(tBu)2H)3Si9 − (1 a) and (Si(tBu)2H)2Si9 2− (2 a) with the highest known number of ligand-free silicon atoms is reported for the first time. The new anions are obtained in a one-step reaction of K12Si17/NH3(liq.) and Si(tBu)2HCl/THF. Electrospray ionization spectrometry and 1H, 13C, 29Si, as well as 29Si-HMBC (heteronuclear multiple bond correlation) NMR spectroscopy, confirm the attachment of three silyl groups at a [Si9]4− cluster under formation of 1 a, in accordance with calculated NMR shifts. During crystal growth the siliconoid di-anion 2 a is formed. The single-crystal X-ray structure determination reveals that two silyl groups are connected to the deltahedral Si9 cluster core, revealing seven unsubstituted exposed silicon cluster atoms with a hemispheroidal coordination. The negative charges −1 and −2 are delocalized over the six and seven siliconoid Si atoms in 1 a and 2 a, respectively.
Description
Keywords
cluster compounds, functionalization, quantum chemical calculations, silicon, siliconoids, synthesis
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Citation
Schiegerl , L J , Karttunen , A J , Klein , W & Fässler , T F 2018 , ' Anionic Siliconoids from Zintl Phases : R 3 Si 9 − with Six and R 2 Si 9 2− with Seven Unsubstituted Exposed Silicon Cluster Atoms (R=Si(tBu) 2 H) ' , Chemistry: A European Journal , vol. 24 , no. 72 , pp. 19171-19174 . https://doi.org/10.1002/chem.201805442