TY - DATA T1 - Stoichiometric and Catalytic Aryl–Perfluoroalkyl Coupling at Tri-tert-butylphosphine Palladium(II) Complexes PY - 2017/08/11 AU - Devin M. Ferguson AU - James R. Bour AU - Allan J. Canty AU - Jeff W. Kampf AU - Melanie S. Sanford UR - https://acs.figshare.com/articles/dataset/Stoichiometric_and_Catalytic_Aryl_Perfluoroalkyl_Coupling_at_Tri-_i_tert_i_-butylphosphine_Palladium_II_Complexes/5305447 DO - 10.1021/jacs.7b05216.s002 L4 - https://ndownloader.figshare.com/files/9112957 KW - Pd KW - CF 2 CF 3 KW - II KW - CF 2 CF 3 ligand KW - TMSCF 2 CF 3 KW - DFT KW - CF 3 analogue KW - side products limits KW - CF 3 KW - α- fluoride elimination N2 - This Communication describes studies of Ph–RF (RF = CF3 or CF2CF3) coupling at Pd complexes of general structure (PtBu3)­PdII(Ph)­(RF). The CF3 analogue participates in fast Ph-CF3 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 PdII complex. Furthermore, they show that this undesired pathway can be circumvented by changing from a CF3 to a CF2CF3 ligand. Ultimately, the insights gained from stoichiometric studies enabled the identification of Pd­(PtBu3)2 as a catalyst for the Pd-catalyzed cross-coupling of aryl bromides with TMSCF2CF3 to afford pentafluoroethylated arenes. ER -