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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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Bibliographic Details
Main Authors: You, Lijun (Author) , Ansmann, Nils (Author) , Greb, Lutz (Author)
Format: Article (Journal)
Language:English
Published: 2025
In: Angewandte Chemie. International edition
Year: 2025, Pages: 1-7
ISSN:1521-3773
DOI:10.1002/anie.202519355
Online Access:Verlag, kostenfrei, Volltext: https://doi.org/10.1002/anie.202519355
Verlag, kostenfrei, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202519355
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Author Notes:Lijun You, Nils Ansmann, and Lutz Greb
Description
Summary: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.
Item Description:Zuerst veröffentlicht: 25. Oktober 2025
Gesehen am 01.12.2025
Physical Description:Online Resource
ISSN:1521-3773
DOI:10.1002/anie.202519355

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