Fontana, Nicolo and Bauer, Jonathan O. (2023) A Cyclic Phosphonium Ion with an Asymmetrically Substituted Selenide-Stabilized Silicon Center: Synthesis, Structure, and Substituent Effects. CHEMISTRYSELECT, 8 (26): e202301373. ISSN 2365-6549,
Full text not available from this repository. (Request a copy)Abstract
A new heterocyclic four-membered CPSeSi cation was synthesized in its racemic form by B(C6F5)(3)-mediated ring-closing reaction starting from the hydrosilane precursor. The cation has an asymmetrically substituted silicon center, which is stabilized by a selenium-silicon bond. The phosphonium hydroborate and its precursor were characterized by single-crystal X-ray diffraction analysis and NMR spectroscopy. Se-77, P-31, and Si-29 NMR spectroscopic parameters proved to be sensitive probes for determining small electronic changes around the silylium-type center. Density functional theory (DFT) calculations of the ring-opening energy of the selenium-based cation gave insight into the stability of the Se-Si bond and revealed a stronger intramolecular stabilization of the silicon atom compared to a coordinating phosphane sulfide function. For the first time, the influence of a C6F5 group at the silicon atom of these type of cations was also investigated, showing a slightly increased stabilization of the Se-Si linkage in the cyclic selenium-based cation.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | CHIRAL MEMORY; CATIONS; Cations; Inorganic rings; Selenium; Silicon; Structure elucidation |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 09 Mar 2024 16:41 |
| Last Modified: | 09 Mar 2024 16:41 |
| URI: | https://pred.uni-regensburg.de/id/eprint/59459 |
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