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Role of silver salts in palladium-catalyzed arene and heteroarene C-H functionalization reactions

Citation

Lotz, MD and Camasso, NM and Canty, AJ and Sanford, MS, Role of silver salts in palladium-catalyzed arene and heteroarene C-H functionalization reactions, Organometallics, 36, (1) pp. 165-171. ISSN 0276-7333 (2017) [Refereed Article]

Copyright Statement

Copyright 2016 American Chemical Society

DOI: doi:10.1021/acs.organomet.6b00437

Abstract

Silver carboxylate salts are widely used as additives in palladium-catalyzed C−H functionalization reactions. However, the role of these silver additives is often not fully understood. This paper describes an investigation of the role of AgOPiv in the stoichiometric activation of C6F5H at a well-defined PdII complex as well as in the PdII-catalyzed oxidative dimerization of 2-alkylthiophenes. Both in situ NMR spectroscopy and H/D exchange studies of the reactions of C6F5H implicate a role for AgOPiv in the C−H cleavage event, generating Ag−C6F5 as an intermediate. The catalytic studies show similar trends despite the different conditions and substrates, suggesting that AgOPiv promotes a similar metalation of the thiophene in the catalytic transformations. This proposal is supported by DFT calculations, which show energetically feasible pathways for concerted metalation−deprotonation of both 2- methylthiophene and pentafluorobenzene at [Ag(OPiv)]2. These studies suggest that initial metalation of C−H substrates at AgI carboxylates should be considered as a plausible pathway in C−H functionalization reactions involving mixtures of Ag and Pd salts.

Item Details

Item Type:Refereed Article
Keywords:silver catalysis, CH activation, CMD, DFT
Research Division:Chemical Sciences
Research Group:Other Chemical Sciences
Research Field:Organometallic Chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Chemical Sciences
Author:Canty, AJ (Professor Allan Canty)
ID Code:115330
Year Published:2017
Web of Science® Times Cited:13
Deposited By:Chemistry
Deposited On:2017-03-17
Last Modified:2017-05-02
Downloads:0

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