Aluminum has been reported to catalyze halodefluorination reactions, where aliphatic fluorine is substituted with a heavier halogen. Although it is known that stoichiometric aluminum halide can perform this reaction, the role of catalytic aluminum halide and organyl alane reagents is not well understood. We investigate the mechanism of the halodefluorination reaction using catalytic aluminum halide and stoichiometric trimethylsilyl halide. We explore the use of B(CF) as a catalyst to benchmark pathways where aluminum acts either as a Lewis acid catalyst in cooperation with trimethylsilyl halide or as an independent halodefluorination reagent which is subsequently regenerated by trimethylsilyl halide. Computational and experimental results indicate that aluminum acts as an independent halodefluorination reagent and that reactivity trends observed between different halide reagents can be attributed to relative barriers in halide delivery to the organic fragment, which is the rate-limiting step in both the aluminum halide- and B(CF)-catalyzed pathways.
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