This Communication describes studies of Ph-R (R = CF or CFCF) coupling at Pd complexes of general structure (PBu)Pd(Ph)(R). The CF analogue participates in fast Ph-CF coupling (<5 min at 80 °C). However, the formation of side products limits the yield of this transformation as well as its translation to catalysis. DFT and experimental studies suggest that the side products derive from facile α-fluoride elimination at the 3-coordinate Pd complex. Furthermore, they show that this undesired pathway can be circumvented by changing from a CF to a CFCF ligand. Ultimately, the insights gained from stoichiometric studies enabled the identification of Pd(PBu) as a catalyst for the Pd-catalyzed cross-coupling of aryl bromides with TMSCFCF to afford pentafluoroethylated arenes.
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