Computational ligand design for the reductive elimination of ArCF₃ from a small bite angle Pd(II) complex: remarkable effect of a perfluoroalkyl phosphine.

To date only three ligands are known to trigger the challenging reductive elimination of ArCF3 from Pd(II). We report the computational design of a bidentate trifluoromethylphosphine ligand that although exhibiting a generally ineffective small bite angle is predicted to give facile reductive elimination. Our experimental verification gave quantitative formation of ArCF3 at 80 °C within 2 h. This highlights the distinct effect of P-CF3 in organometallic reactivity and constitutes a proof-of-principle study of computational reactivity design.