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Updated: Oct 4, 2025
![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
Copper(I) activation of C-X bonds: bimolecular vs. unimolecular reaction mechanism
Guillermo Marcos-Ayuso1, Agustí Lledós2, Juan A Casares1
1IU CINQUIMA/Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, 47011-Valladolid, Spain. juanangel.casares@uva.es.
Abstract:
Experimental kinetic studies and DFT calculations show that the oxidative addition of aryl halides (Ar-X) to complexes [Cu(NHC)R] follow different paths depending on the nature of X. For X = Br a concerted addition leads to cis-[Cu(NHC)XRAr] from which the usual C-C coupled product Ar-R eliminates. However, for X = I trans-[Cu(NHC)IRAr] is formed instead, leading to the elimination of R-I in a metathesis reaction. This behaviour is accounted for by a change in the reaction mechanism for Ar-I, which involves two molecules of copper(I) complex, the second one stabilising the incipient iodide formed in the C-I breaking (oxidative addition) and C-I forming (reductive elimination) processes.
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