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Silylenes with a Small Chalcogenide Substituent: Tuning Frontier Orbital Energies from O to Te

Müller, Maximilian P. 1; Hinz, Alexander ORCID iD icon 1
1 Institut für Anorganische Chemie (AOC), Karlsruher Institut für Technologie (KIT)

Abstract:

The general synthesis of heteroleptic acyclic silylenes with a bulky carbazolyl substituent ($^{dtbp}$Cbz) is detailed and a series of compounds with a chalcogenide substituent of the type [($^{dtbp}$Cbz)SiE$^{16}$R] (E$^{16}$R=O$^t$Bu, SEt, SePh, TePh) is reported. With the bulky carbazolyl substituent present, the chalcogenide moiety can be very small, as is shown by incorporating groups as small as ethyl, phenyl or tert-butyl. For the first time, the electronic properties of the silylene can be tuned along a complete series of chalcogenide substituents. The effects are clearly visible in the NMR and UV/Vis spectra, and were rationalised by DFT computations. The reactivity of the heaviest chalcogenide-substituted silylenes was probed by reactions with trimethylphosphine selenide and the terphenyl azide TerN$_3$ (Ter=2,6-dimesitylphenyl).


Verlagsausgabe §
DOI: 10.5445/IR/1000171554
Veröffentlicht am 13.06.2024
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Anorganische Chemie (AOC)
Publikationstyp Zeitschriftenaufsatz
Publikationsjahr 2024
Sprache Englisch
Identifikator ISSN: 1433-7851, 0570-0833, 1521-3773
KITopen-ID: 1000171554
Erschienen in Angewandte Chemie - International Edition
Verlag John Wiley and Sons
Band 63
Heft 28
Seiten Art.-N.r: e202405319
Vorab online veröffentlicht am 24.04.2024
Nachgewiesen in Web of Science
Dimensions
Scopus
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