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Ligand Redox Reactivity Supports C-F Activation at Al(III)
Shuyu Xu1, Keyan Li1, Nathan Phan1
1Department of Chemistry, University of California, Davis, California95616, United States.
None:
C-F bond activation has applications in organic synthesis, and known pathways include two- or one-electron reduction of the C-F bond, and fluoride abstraction. Low-valent aluminum(I) complexes are known to activate C-F bonds via an oxidative addition mechanism. Here, we report a stoichiometric activation of C-F bonds in aryl-CF3 compounds using an Al(III) complex that is supported by a two-electron redox change on the supporting noninnocent ligand. The overall reaction observed involves a two-electron ligand-based oxidation along with the formation of two Al-F bonds to afford [(PhI2P0)AlF2]+ from (PhI2P2-)AlI, where PhI2P is a diiminepyridine ligand. Possible intermediates including a radical species (PhI2P-)AlF2 and a fully oxidized [(PhI2P0)AlI2]+ were synthesized and characterized to better understand the relationship between ligand redox chemistry and C-F bond activation.
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