title: Ligand-dependent formation of ion-pair CuI/CuIIItrifluoromethyl complexes containing bisphosphines.
abstract: We report novel ion-pair bisphosphine CuI/CuIIItrifluoromethyl complexes [(P2)2CuI]+[CuIII(CF3)4]-(P2= DPPE, BINAP or Xantphos) featuring tetrahedral CuIand square planar CuIIIunits that are prepared via oxidative trifluoromethylation of CuI with CF3SiMe3in the presence of AgF. The bisphosphine CuI/CuIIICF3complexes 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/CuIIIcomplex with phen/PPh3ligands (1'). These results not only provide strong evidence that both the neutral and ion-pair CuIIICF3complexes 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.
authors.affiliation: The Key Laboratory of Food Colloids and Biotechnology, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, Jiangsu Province, China. slzhang@jiangnan.edu.cn.
authors.forename: Song-Lin
authors.initials: SL
authors.lastname: Zhang
authors.forename: Wen-Feng
authors.initials: WF
authors.lastname: Bie