Amplifying Lewis acidity by oxidation

• Verfasst von: Thorwart, Thaddäus [VerfasserIn]
• Verfasst von: Schmitt, Manuel [VerfasserIn]
• Verfasst von: Greb, Lutz [VerfasserIn]
• Titel: Amplifying Lewis acidity by oxidation
• Titelzusatz: leveraging the redox-activity of bis(3,6-di-tert-butyl-catecholato)silane
• Verf.angabe: Thaddäus Thorwart, Manuel Schmitt and Lutz Greb
• E-Jahr: 2025
• Jahr: 07 January 2025
• Umfang: 5 S.
• Illustrationen: Illustrationen
• Fussnoten: Online verfügbar: 29. November 2024 ; Gesehen am 06.06.2025
• Titel Quelle: Enthalten in: Dalton transactions
• Ort Quelle: Cambridge : Royal Society of Chemistry, 2003
• Jahr Quelle: 2025
• Band/Heft Quelle: 54(2025), 1, Seite 65-69
• ISSN Quelle: 1477-9234
• DOI: doi:10.1039/D4DT03176H
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1927795249

Abstract

Bis(catecholato)silanes were showcased as strong Lewis acids, while their inherent redox activity remained unexplored in this context. In the present work, we study the oxidation of monomeric bis(3,6-di-tert-butyl-catecholato)silane (1), leading to the Lewis superacidic radicalic silylium ionradical 1˙+ (FIA 784 kJ mol−1). Oxidation of 1 with [N(p-C6H4Br)3][B(C6F5)4] yielded [1][B(C6F5)4], displaying strong catalytic activity in the Friedel-Crafts-dimerization, hydrodeoxygenation and carbonyl-olefin-metathesis. It demonstrates how Lewis acidity can be amplified through oxidation without needing an add-on redox-active substituent. Instead, it synergizes the constraining effect of catecholates with their inherent redox non-innocence to unlock enhanced catalytic performance.