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A chemoselective C(sp2)F or C(sp3)F bond activation of hexafluoropropylene (HFP) was achieved by adopting the proper combination of a Lewis acid co‐additive with a ligand which coordinates Pd0. The treatment of [(η2‐HFP)Pd(PCy3)2] with B(C6F5)3 allowed a chemoselective C(sp3)F bond cleavage of HFP to give a unique cationic perfluoroallypalladium complex. In this complex, the coordination mode of...
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