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Transmetalation Reactions Triggered by Electron Transfer between Organocopper Complexes

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journal contribution
posted on 14.07.2021, 14:33 by Olmo Lozano-Lavilla, Pablo Gómez-Orellana, Agustí Lledós, Juan A. Casares
[Cu­(bipy)­(C6F5)] 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)­(C6F5)] 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.