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 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 )-C(sp)N bond forming reaction is characterized herein, for the first time, complementing previous studies reported for C(sp )-C(sp ), C(sp )-C(sp ), and C(sp )-C(sp ) bond formation processes taking place on gold(III) species.
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