Pd(0), Pd(II) electromerism triggered by Lewis base coordination to a redox-active silicon Z-type ligand
Electromerism (aka. valence tautomerism) corresponds to the switching of electronic distributions between redox-active ligands and central elements. While this phenomenon is well established for several transition metals, the Pd(0)/Pd(II) couple could not yet be involved due to the high energy of th...
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| Main Authors: | , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
27 January 2025
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| In: |
Angewandte Chemie. International edition
Year: 2025, Volume: 64, Issue: 5, Pages: 1-7 |
| ISSN: | 1521-3773 |
| DOI: | 10.1002/anie.202417581 |
| Online Access: | Verlag, kostenfrei, Volltext: https://doi.org/10.1002/anie.202417581 Verlag, kostenfrei, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202417581 
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| Author Notes: | Nils Ansmann, Marion Kerscher, Lutz Greb |
| Summary: | Electromerism (aka. valence tautomerism) corresponds to the switching of electronic distributions between redox-active ligands and central elements. While this phenomenon is well established for several transition metals, the Pd(0)/Pd(II) couple could not yet be involved due to the high energy of the Pd(0) state. In this study, we present Pd(0)/Pd(II) electromerism by using a redox-active bis(phosphanyl-amidophenolato)silane. Strong silicon-based Z-type interaction stabilizes the Pd(0) state with an oxidized dicationic open-shell singlet ligand while binding of a Lewis base at the Lewis acidic silicon results in the loss of Z-type interaction and the intramolecular rearrangement to the Pd(II)/reduced ligand electromer. It introduces a novel concept for spin state switching by combining ligand ambiphilicity and redox activity. |
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| Item Description: | Gesehen am 18.03.2025 Online veröffentlicht: 24. Dezember 2024 |
| Physical Description: | Online Resource |
| ISSN: | 1521-3773 |
| DOI: | 10.1002/anie.202417581 |