"The copper-catalysed functionalization of aryl halides is one of the most preferred methods for the formation of carbon-carbon and carbon-heteroatom bonds.1 Yet, the redox behaviour of the copper species in the catalytic cycle remains elusive and a subject of considerable debate.2 We report experimental and theoretical mechanistic investigations into the reaction of a well-defined Cu(I) complex with an electron-poor aryl iodide, which leads to the formation of an isolable Cu(III)aryl complex, that subsequently reductively eliminates to forge a C(sp2)CF3 bond."
"Our integrated experimental and theoretical findings indicate that the process proceeds through a redox sequence of Cu(I)/Cu(III)/Cu(II)/Cu(III)/Cu(I). Additionally, we managed to interrupt this sequence by temperature control and captured the reactivity of the copper species through various spectroscopic methods, facilitating in-depth mechanistic analysis. These findings shed light on the intricate behaviour of copper species and challenge the traditional mechanistic proposal for the reaction of Cu(I) with aryl iodide, thus providing fresh perspectives into the mechanistic aspect of the copper-catalysed coupling reactions."
Reactions of a well-defined Cu(I) complex with an electron-poor aryl iodide produce an isolable Cu(III)aryl complex that undergoes reductive elimination to form a C(sp2)-CF3 bond. Integrated experimental and theoretical analyses indicate the catalytic cycle follows a redox sequence of Cu(I)/Cu(III)/Cu(II)/Cu(III)/Cu(I). Temperature control enabled interruption of the redox sequence and isolation or spectroscopic detection of intermediate copper species. Various spectroscopic methods were used to capture the reactivity and allow in-depth mechanistic analysis. The observed redox behaviour challenges traditional mechanistic proposals for Cu(I) reaction with aryl iodides and offers new perspectives for copper-catalysed coupling reactions.
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