Light-Driven Hydrodefluorination of Electron-Rich Aryl Fluorides by an Anionic Rhodium-Gallium Photoredox Catalyst.

ABSTRACT: An anionic Rh-Ga complex catalyzed the hydrodefluorination of challenging C-F bonds in electron-rich aryl fluorides and trifluoromethylarenes when irradiated with violet light in the presence of H₂ , a stoichiometric alkoxide base, and a crown-ether additive. Based on theoretical calculations, the lowest unoccupied molecular orbital (LUMO), which is delocalized across both the Rh and Ga atoms, becomes singly occupied upon excitation, thereby poising the Rh-Ga complex for photoinduced single-electron transfer (SET). Stoichiometric and control reactions support that the C-F activation is mediated by the excited anionic Rh-Ga complex. After SET, the proposed neutral Rh⁰ intermediate was detected by EPR spectroscopy, which matched the spectrum of an independently synthesi

SUBMITTER: Moore JT 

PROVIDER: S-EPMC9826370 | biostudies-literature | 2022 Oct

REPOSITORIES: biostudies-literature