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Mechanistic Insights into C(sp2)−C(sp)N Reductive Elimination from Gold(III) Cyanide Complexes


Genoux, Alexandre; González, Jorge A; Merino, Estíbaliz; Nevado, Cristina (2020). Mechanistic Insights into C(sp2)−C(sp)N Reductive Elimination from Gold(III) Cyanide Complexes. Angewandte Chemie Internationale Edition, 59(41):17881-17886.

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.

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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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > Catalysis
Physical Sciences > General Chemistry
Uncontrolled Keywords:General Chemistry, Catalysis
Language:English
Date:5 October 2020
Deposited On:09 Feb 2021 10:06
Last Modified:10 Feb 2021 21:00
Publisher:Wiley-VCH Verlag
ISSN:1433-7851
OA Status:Closed
Publisher DOI:https://doi.org/10.1002/anie.202005731
PubMed ID:32648359
Project Information:
  • : FunderFP7
  • : Grant ID307948
  • : Project TitleNIGOCAT - Nature-Inspired Gold Catalytic Tools
  • : FunderSNSF
  • : Grant ID200020_146853
  • : Project TitleNovel Synthetic Methods based on Gold Catalyzed Reactions

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Embargo till: 2021-07-10