Reversible oxidative addition of nonactivated C-H bonds to structurally constrained phosphenium ions

• Verfasst von: Roth, Daniel [VerfasserIn]
• Verfasst von: Radosevich, Alexander T. [VerfasserIn]
• Verfasst von: Greb, Lutz [VerfasserIn]
• Titel: Reversible oxidative addition of nonactivated C-H bonds to structurally constrained phosphenium ions
• Verf.angabe: Daniel Roth, Alexander T. Radosevich, and Lutz Greb
• E-Jahr: 2023
• Jahr: October 25, 2023
• Umfang: 7 S.
• Illustrationen: Illustrationen
• Fussnoten: Gesehen am 29.11.2023
• Titel Quelle: Enthalten in: American Chemical SocietyJournal of the American Chemical Society
• Ort Quelle: Washington, DC : ACS Publications, 1879
• Jahr Quelle: 2023
• Band/Heft Quelle: 145(2023), 44, Seite 24184-24190
• ISSN Quelle: 1520-5126
• DOI: doi:10.1021/jacs.3c08456
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1871582199

Abstract

A series of structurally constrained phosphenium ions based on pyridinylmethylamidophenolate scaffolds are shown to undergo P(III)/P(V) oxidative addition with C-H bonds of alkynes, alkenes, and arenes. Nonactivated substrates such as benzene, toluene, and deactivated chlorobenzene are phosphorylated in quantitative yields. Computational and spectroscopic studies suggest a low-barrier isomerization from a bent to a T-shaped isomer that initiates a phosphorus-ligand-cooperative pathway and subsequent ring-chain tautomerism. Remarkably, C-H bond activations occur reversibly, allowing for reductive elimination back to P(III) at elevated temperatures or the exchange with other substrates.