Silylenes with a small chalcogenide substituent: Tuning frontier orbital energies from O to Te

Maximilian P Müller; Alexander Hinz

doi:10.1002/anie.202405319

Silylenes with a small chalcogenide substituent: Tuning frontier orbital energies from O to Te

Angew Chem Int Ed Engl. 2024 Apr 24:e202405319. doi: 10.1002/anie.202405319. Online ahead of print.

Authors

Maximilian P Müller¹, Alexander Hinz²

Affiliations

¹ Karlsruhe Institute of Technology, Institute for Inorganic Chemistry, GERMANY.
² Karlsruher Institut fur Technologie, Institut fur Anorganische Chemie, Engesserstr. 15, Gebaude 30.45, 76131, Karlsruhe, GERMANY.

PMID: 38656624
DOI: 10.1002/anie.202405319

Abstract

The general synthesis of heteroleptic acyclic silylenes with a bulky carbazolyl substituent (dtbpCbz) is detailed and a series of compounds with a chalcogenide substituent of the type [(dtbpCbz)SiE16R] (E16R = OtBu, 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 TerN3 (Ter = 2,6-dimesitylphenyl).

Keywords: Acyclic Silylenes; Bonding; Frontier Orbitals; Low-Valent Main Group; reactivity.