dc.contributor.author
Poleschner, Helmut
dc.contributor.author
Seppelt, Konrad
dc.date.accessioned
2021-01-07T13:27:28Z
dc.date.available
2021-01-07T13:27:28Z
dc.identifier.uri
https://refubium.fu-berlin.de/handle/fub188/28804
dc.identifier.uri
http://dx.doi.org/10.17169/refubium-28553
dc.description.abstract
Thiiranium salts [Ad(2)SR]X-+(-)(5,8,9,11,12; X-=Tf2N-(Tf=CF3SO2), SbCl6-) and seleniranium salts [Ad(2)SeR]X-+(-)(14,16,17,23-25; X-=Tf2N-, BF4-, CHB11Cl11-, SbCl6-) are synthesized from strained alkene bis(adamantylidene) (1). The disulfides and the diselenides (Me3SiCH2CH2E)(2)(4,13), (tBuMe(2)SiCH(2)CH(2)E)(2)(7,22), and (NCCH2CH2E)(2)(10,15; E=S, Se) have been used. The thiirenium salts [tBu(2)C(2)SR]X-+(-)(34) and [Ad(2)C(2)SR]X-+(-)(35,36) are prepared from the bis-tert-butylacetylene (2) and bis-adamantyl-acetylene (3) with R=Me(3)SiCH(2)CH(2)andtBuMe(2)SiCH(2)CH(2). Attempts to cleave off the groups Me3SiCH2CH2,tBuMe(2)SiCH(2)CH(2), and NCCH(2)CH(2)resulted in thiiranes27,30. No selenirane Ad(2)Se (33) is formed from seleniranium salts, instead cleavage to the alkene (1) and diselenide (13,15) occurs. The thiirenium salt [Ad(2)C(2)SCH(2)CH(2)SiMe(3)]+Tf2N-(35) does not yield the thiirene Ad(2)C(2)S (37), the three-membered ring is cleaved, forming the alkyne (3) and disulfide (4). All compounds are characterized by ESI mass spectra, NMR spectra, and by quantum chemical calculations. Crystal structures of the salts8,12,25,17,26,36and the thiiranes27,30are presented.
en
dc.format.extent
12 Seiten
dc.rights.uri
https://creativecommons.org/licenses/by-nc-nd/4.0/
dc.subject
ab-initio calculations
en
dc.subject
NMR spectroscopy
en
dc.subject
X-ray diffraction
en
dc.subject.ddc
500 Naturwissenschaften und Mathematik::540 Chemie::546 Anorganische Chemie
dc.title
Attempts to Synthesize a Thiirane, Selenirane, and Thiirene by Dealkylation of Chalcogeniranium and Thiirenium Salts
dc.type
Wissenschaftlicher Artikel
dcterms.bibliographicCitation.doi
10.1002/chem.202003461
dcterms.bibliographicCitation.journaltitle
Chemistry - A European Journal
dcterms.bibliographicCitation.number
2
dcterms.bibliographicCitation.pagestart
649
dcterms.bibliographicCitation.pageend
659
dcterms.bibliographicCitation.volume
27
dcterms.bibliographicCitation.url
https://doi.org/10.1002/chem.202003461
refubium.affiliation
Biologie, Chemie, Pharmazie
refubium.affiliation.other
Institut für Anorganische Chemie
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refubium.funding
DEAL Wiley
refubium.resourceType.isindependentpub
no
dcterms.accessRights.openaire
open access
dcterms.isPartOf.eissn
1521-3765
refubium.resourceType.provider
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