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

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dc.contributorAalto-yliopistofi
dc.contributorAalto Universityen
dc.contributor.authorSchiegerl, Lorenz J.en_US
dc.contributor.authorKarttunen, Antti J.en_US
dc.contributor.authorKlein, Wilhelmen_US
dc.contributor.authorFässler, Thomas F.en_US
dc.contributor.departmentDepartment of Chemistry and Materials Scienceen
dc.contributor.groupauthorInorganic Materials Modellingen
dc.contributor.organizationTechnische Universität Münchenen_US
dc.date.accessioned2019-01-14T09:18:13Z
dc.date.available2019-01-14T09:18:13Z
dc.date.embargoinfo:eu-repo/date/embargoEnd/2019-12-31en_US
dc.date.issued2018-12-20en_US
dc.description.abstractNeutral 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.en
dc.description.versionPeer revieweden
dc.format.extent4
dc.format.extent19171-19174
dc.format.mimetypeapplication/pdfen_US
dc.identifier.citationSchiegerl, 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.201805442en
dc.identifier.doi10.1002/chem.201805442en_US
dc.identifier.issn0947-6539
dc.identifier.issn1521-3765
dc.identifier.otherPURE UUID: 00cfff38-bff6-4e7e-affe-2d4f41dc8157en_US
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dc.identifier.otherPURE LINK: http://www.scopus.com/inward/record.url?scp=85058298804&partnerID=8YFLogxKen_US
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dc.identifier.urihttps://aaltodoc.aalto.fi/handle/123456789/35894
dc.identifier.urnURN:NBN:fi:aalto-201901141077
dc.language.isoenen
dc.relation.ispartofseriesChemistry - A European Journalen
dc.relation.ispartofseriesVolume 24, issue 72en
dc.rightsopenAccessen
dc.subject.keywordcluster compoundsen_US
dc.subject.keywordfunctionalizationen_US
dc.subject.keywordquantum chemical calculationsen_US
dc.subject.keywordsiliconen_US
dc.subject.keywordsiliconoidsen_US
dc.subject.keywordsynthesisen_US
dc.titleAnionic Siliconoids from Zintl Phases: R3Si9 − with Six and R2Si9 2− with Seven Unsubstituted Exposed Silicon Cluster Atoms (R=Si(tBu)2H)en
dc.typeA1 Alkuperäisartikkeli tieteellisessä aikakauslehdessäfi
dc.type.versionpreprint
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