Pd(0), Pd(II) electromerism triggered by Lewis base coordination to a redox-active silicon Z-type ligand

• Verfasst von: Ansmann, Nils [VerfasserIn]
• Verfasst von: Kerscher, Marion [VerfasserIn]
• Verfasst von: Greb, Lutz [VerfasserIn]
• Titel: Pd(0), Pd(II) electromerism triggered by Lewis base coordination to a redox-active silicon Z-type ligand
• Verf.angabe: Nils Ansmann, Marion Kerscher, Lutz Greb
• E-Jahr: 2025
• Jahr: 27 January 2025
• Umfang: 7 S.
• Fussnoten: Gesehen am 18.03.2025 ; Online veröffentlicht: 24. Dezember 2024
• Titel Quelle: Enthalten in: Angewandte Chemie. International edition
• Ort Quelle: Weinheim : Wiley-VCH, 1998
• Jahr Quelle: 2025
• Band/Heft Quelle: 64(2025), 5 vom: Jan., Artikel-ID e202417581, Seite 1-7
• ISSN Quelle: 1521-3773
• DOI: doi:10.1002/anie.202417581
• Datenträger: Online-Ressource
• Sprache: eng
• Sach-SW: electromerism
• Sach-SW: palladium
• Sach-SW: silicon
• Sach-SW: valence tautomerism
• Sach-SW: Z-type ligand
• K10plus-PPN: 191999419X

Abstract

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.