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.
ETH Zürich, Laboratory for Organic Chemistry, Vladimir-Prelog-Weg 3, 8093 Zürich (Switzerland).
Mads C
MC
Nielsen
Karl J
KJ
Bonney
Franziska
F
Schoenebeck
computational chemistry; ligand effects; palladium; reductive elimination; trifluoromethylation