Mechanistic Insights into C(sp2)−C(sp)N Reductive Elimination from Gold(III) Cyanide Complexes |
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| Authors: | Alexandre Genoux Dr Jorge A González Dr Estíbaliz Merino Prof Dr Cristina Nevado |
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| Institution: | Department of Chemistry, University of Zurich, Winterthurerstrasse 190, 8057 Zürich, Switzerland |
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| 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. |
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| Keywords: | asynchronous cyanide gold(III) kinetic study reductive elimination |
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