Department of Chemistry, University of Zurich, Winterthurerstrasse 190, 8057, Zürich, Switzerland.
Current address: Department of Organic and Inorganic Chemistry, Chemical Research Institute Andrés M. del Río (IQAR) University of Alcalá, 28805, Alcalá de Henares, Madrid, Spain.
Angew Chem Int Ed Engl. 2020 Oct 5;59(41):17881-17886. doi: 10.1002/anie.202005731. Epub 2020 Aug 13.
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.
一个新的膦配体二氰基芳基金（III）配合物家族已经被制备出来，并对其还原消除反应的活性进行了详细研究。高正的活化熵和初级的 C 同位素效应都表明存在一个晚期协同过渡态，而哈梅特分析和密度泛函理论计算则表明该过程是异步的。因此，本文首次描述了一种独特的机制，涉及整体 C(sp )-C(sp)N 键形成反应的异步协同还原消除，补充了以前报道的在金（III）物种上发生的 C(sp )-C(sp )、C(sp )-C(sp )和 C(sp )-C(sp )键形成过程的研究。
