Inverting palladium-phosphorus Lewis pair formation: phosphonium acting as Z-type ligand
Phosphorus-based ligands are prototypical L-type donors. Here, we introduce a Lewis acidic phosphonium cation that engages in unprecedented Z-type coordination to palladium(0). The resulting Pd→P(V) interactions are structurally unique and stronger than conventional L-type Pd─phosphine bonds, as rev...
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| Hauptverfasser: | , , |
|---|---|
| Dokumenttyp: | Article (Journal) |
| Sprache: | Englisch |
| Veröffentlicht: |
2025
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| In: |
Angewandte Chemie. International edition
Year: 2025, Pages: 1-7 |
| ISSN: | 1521-3773 |
| DOI: | 10.1002/anie.202519355 |
| Online-Zugang: | Verlag, kostenfrei, Volltext: https://doi.org/10.1002/anie.202519355 Verlag, kostenfrei, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202519355 |
| Verfasserangaben: | Lijun You, Nils Ansmann, and Lutz Greb |
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| 520 | |a Phosphorus-based ligands are prototypical L-type donors. Here, we introduce a Lewis acidic phosphonium cation that engages in unprecedented Z-type coordination to palladium(0). The resulting Pd→P(V) interactions are structurally unique and stronger than conventional L-type Pd─phosphine bonds, as revealed by NMR spectroscopy, x-ray crystallography, and quantum chemical analyses (NBO, ETS-NOCV, and QTAIM). It enables the formation of rare L2Z-type Pd(0) complexes with distinctive optical and electronic properties. A notably mild P─C bond forming reaction suggests an overlooked role of Z-type interactions for facilitating reductive elimination pathways. | ||
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