Mechanistic Insights into C(sp<sup>2</sup>)−C(sp)N Reductive Elimination from Gold(III) Cyanide Complexes
Alexandre Genoux, Jorge A. González, Estı́baliz Merino, Cristina Nevado
Abstract
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 12/13 C 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(sp 2 )−C(sp)N bond forming reaction is characterized herein, for the first time, complementing previous studies reported for C(sp 3 )−C(sp 3 ), C(sp 2 )−C(sp 2 ), and C(sp 3 )−C(sp 2 ) bond formation processes taking place on gold(III) species.