We report novel ion-pair bisphosphine CuI/CuIII trifluoromethyl complexes [(P2)2CuI]+[CuIII(CF3)4]- (P2 = DPPE, BINAP or Xantphos) featuring tetrahedral CuI and square planar CuIII units that are prepared via oxidative trifluoromethylation of CuI with CF3SiMe3 in the presence of AgF. The bisphosphine CuI/CuIII CF3 complexes are highly reactive for aerobic trifluoromethylation of arylboronic acids to produce trifluoromethylated arenes in good to quantitative yields, which is in sharp contrast to the CuI/CuIII complex with phen/PPh3 ligands (1'). These results not only provide strong evidence that both the neutral and ion-pair CuIII CF3 complexes are competent catalytic species for Cu-mediated oxidative trifluoromethylation reactions, but also have important mechanistic implications that the active catalyst and reaction mechanism should be distinct and ligand-dependent for trifluoromethylation reactions with different types of ancillary ligands VSports手机版. .