Anionic Siliconoids from Zintl Phases: R3Si9 with Six and R2Si9 2− with Seven Unsubstituted Exposed Silicon Cluster Atoms (R=Si(tBu)2H)

Lorenz J. Schiegerl, Antti J. Karttunen, Wilhelm Klein, Thomas F. Fässler*

*Tämän työn vastaava kirjoittaja

Tutkimustuotos: LehtiartikkeliArticleScientificvertaisarvioitu

6 Sitaatiot (Scopus)
43 Lataukset (Pure)

Abstrakti

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.

AlkuperäiskieliEnglanti
Sivut19171-19174
Sivumäärä4
JulkaisuChemistry - A European Journal
Vuosikerta24
Numero72
DOI - pysyväislinkit
TilaJulkaistu - 20 joulukuuta 2018
OKM-julkaisutyyppiA1 Julkaistu artikkeli, soviteltu

Sormenjälki Sukella tutkimusaiheisiin 'Anionic Siliconoids from Zintl Phases: R<sub>3</sub>Si<sub>9</sub> <sup>−</sup> with Six and R<sub>2</sub>Si<sub>9</sub> <sup>2−</sup> with Seven Unsubstituted Exposed Silicon Cluster Atoms (R=Si(tBu)<sub>2</sub>H)'. Ne muodostavat yhdessä ainutlaatuisen sormenjäljen.

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