Abstract
A new family of phosphine‐ligated dicyanoarylgold(III) complexes has been prepared and their reactivity towards reductive elimination has been studied in detail. Both, a highly positive entropy of activation and a primary 12/13C KIE suggest a late concerted transition state while Hammett analysis and DFT calculations indicate that the process is asynchronous. As a result, a distinct mechanism involving an asynchronous concerted reductive elimination for the overall C(sp2)−C(sp)N bond forming reaction is characterized herein, for the first time, complementing previous studies reported for C(sp3)−C(sp3), C(sp2)−C(sp2), and C(sp3)−C(sp2) bond formation processes taking place on gold(III) species.
Genoux, Alexandre