Jump to main content
Jump to site search


Is silver a mere terminal oxidant in palladium catalyzed C–H bond activation reactions?

Author affiliations

Abstract

In the contemporary practice of palladium catalysis, a molecular understanding of the role of vital additives used in such reactions continues to remain rather vague. Herein, we disclose an intriguing and a potentially general role for one of the most commonly used silver salt additives, discovered through rigorous computational investigations on four diverse Pd-catalyzed C–H bond activation reactions involving sp2 aryl C–H bonds. The catalytic pathways of different reactions such as phosphorylation, arylation, alkynylation, and oxidative cycloaddition are analyzed, with and without the explicit inclusion of the silver additive in the respective transition states and intermediates. Our results indicate that the pivotal role of silver salts is likely to manifest in the form of a Pd–Ag heterobimetallic species that facilitates intermetallic electronic communication. The Pd–Ag interaction is found to provide a consistently lower energetic span as compared to an analogous pathway devoid of such interaction. Identification of a lower energy pathway as well as enhanced catalytic efficiency due to Pd–Ag interaction could have broad practical implications in the mechanism of transition metal catalysis and the current perceptions on the same.

Graphical abstract: Is silver a mere terminal oxidant in palladium catalyzed C–H bond activation reactions?

Back to tab navigation

Supplementary files

Publication details

The article was received on 08 Sep 2019, accepted on 30 Oct 2019 and first published on 13 Nov 2019


Article type: Edge Article
DOI: 10.1039/C9SC04540F
Chem. Sci., 2020, Advance Article
  • Open access: Creative Commons BY-NC license
    All publication charges for this article have been paid for by the Royal Society of Chemistry

  •   Request permissions

    Is silver a mere terminal oxidant in palladium catalyzed C–H bond activation reactions?

    B. Bhaskararao, S. Singh, M. Anand, P. Verma, P. Prakash, A. C, S. Malakar, H. F. Schaefer and R. B. Sunoj, Chem. Sci., 2020, Advance Article , DOI: 10.1039/C9SC04540F

    This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material and it is not used for commercial purposes.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements