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Mechanistic Insights into C(sp 2 )−C(sp)N Reductive Elimination from Gold(III) Cyanide Complexes
Author(s) -
Genoux Alexandre,
González Jorge A.,
Merino Estíbaliz,
Nevado Cristina
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202005731
Subject(s) - reductive elimination , chemistry , cyanide , phosphine , reactivity (psychology) , concerted reaction , reaction mechanism , stereochemistry , medicinal chemistry , catalysis , inorganic chemistry , organic chemistry , medicine , alternative medicine , pathology
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.