Froetschel-Rittmeyer, Julia and Hennersdorf, Felix and Fidelius, Jannis and Sala, Chris and Ziegler, Christoph and Holthausen, Michael and Schwedtmann, Kai and Wolf, Robert and Weigand, Jan J. (2025) Synthesis and Reactivity of Triphosphaallyl Cation Stabilized by N-Heterocyclic Carbenes. CHEMISTRY-A EUROPEAN JOURNAL, 31 (37): e202501311. ISSN 0947-6539, 1521-3765
Full text not available from this repository. (Request a copy)Abstract
Reduction of the triphosphaallyl species 6[GaCl4] with GaI[Ga2Cl7] affords the imidazoliumyl-substituted (L) bicyclo[2.1.1]-triphosphane 10[Ga2Cl7], featuring an unprecedented Ga2Cl5-bridged P3 scaffold. Reactions of 10[Ga2Cl7] with nucleophiles (Cl- or NHC) result in rare, selective P-C bond cleavages, affording Ga2Cly-substituted triphosphiranes (LP3Ga2Cly, y = 5, 6) via an intramolecular ring closure mechanism. Protonation of 6[GaCl4] gives rise to a similar ring closure, but without P-C bond cleavage, to afford the L2P3H+ salt 8[OTfGaCl3]2. Additionally, the palladium complex 26[GaCl4], formed through the reaction of 10[Ga2Cl7] with [Pd(PPh3)4], presents a novel bicyclic P3Pd moiety (LP3Pd(PPh3)2[GaCl4]). Comprehensive DFT calculations have been conducted to elucidate the bonding situation in 26[GaCl4], uncovering significant metal-to-ligand pi-back-donation and a distinctive 3-center-4-electron hyperbonding phenomenon in the P3Pd framework. These findings offer valuable insights into chemistry of cyclic polyphosphorus compounds and, in particular, the reactivity, structural flexibility, and the coordination properties of cationic triphosphorus species.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | MAGNETIC-RESONANCE SPECTRA; CRYSTAL-STRUCTURE; WHITE PHOSPHORUS; MEDIATED FRAGMENTATION; P TRANSFER; CHEMISTRY; COMPLEXES; OXIDATION; ELEMENTS; SODIUM; cyclic phosphorus scaffolds; gallium-phosphorus bonding; N-heterocyclic carbene; P-C bond activation; triphosphaallyl cation |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Arbeitskreis Prof. Dr. Robert Wolf |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 07 May 2026 04:38 |
| Last Modified: | 07 May 2026 04:38 |
| URI: | https://pred.uni-regensburg.de/id/eprint/66804 |
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