%0 Generic %A Ferguson, Devin M. %A Bour, James R. %A Canty, Allan J. %A Kampf, Jeff W. %A Sanford, Melanie S. %D 2017 %T Stoichiometric and Catalytic Aryl–Perfluoroalkyl Coupling at Tri-tert-butylphosphine Palladium(II) Complexes %U https://acs.figshare.com/articles/dataset/Stoichiometric_and_Catalytic_Aryl_Perfluoroalkyl_Coupling_at_Tri-_i_tert_i_-butylphosphine_Palladium_II_Complexes/5305447 %R 10.1021/jacs.7b05216.s002 %2 https://acs.figshare.com/ndownloader/files/9112957 %K Pd %K CF 2 CF 3 %K II %K CF 2 CF 3 ligand %K TMSCF 2 CF 3 %K DFT %K CF 3 analogue %K side products limits %K CF 3 %K α- fluoride elimination %X 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. %I ACS Publications