Transmetalation Reactions Triggered by Electron Transfer between Organocopper Complexes

[Cu(bipy)(CF)] reacts with most aryl iodides to form heterobiphenyls by cross-coupling, but when Rf-I is used (Rf = 3,5-dicholoro-2,4,6-trifluorophenyl), homocoupling products are also formed. Kinetic studies suggest that, for the homocoupling reaction, a mechanism based on transmetalation from [Cu(bipy)(CF)] to Cu(III) intermediates formed in the oxidative addition step is at work. Density functional theory calculations show that the interaction between these Cu(III) species and the starting Cu(I) complex involves a Cu(I)-Cu(III) electron transfer concerted with the formation of an iodine bridge between the metals and that a fast transmetalation takes place in a dimer in a triplet state between two Cu(II) units. In copper-catalyzed cross-coupling reactions, electron-transfer processes between Cu(I) and Cu(III) species are overlooked behind RDS (C−X activation). Density functional theory studies considering two molecules of the catalyst and two spin states throughout the course of the reaction have revealed the feasibility of such a process and the transmetalation between Cu(II) species, justifying in this way the formation of homocoupling products.