Wenzel, Margot Nina, Owens, Philippa Kate, Bray, Joshua Thomas William orcid.org/0000-0003-2384-9675 et al. (7 more authors) (2017) Redox Couple Involving NOx in Aerobic Pd-Catalyzed Oxidation of sp3‑C−H Bonds: Direct Evidence for Pd−NO3−/NO2− Interactions Involved in Oxidation and Reductive Elimination. Journal of the American Chemical Society. pp. 1177-1190. ISSN 1520-5126
Abstract
NaNO3 is used in oxidative Pd-catalyzed processes as a complementary co-catalyst to common oxidants, e.g., CuII salts, in C−H bond activation and Wacker oxidation processes. NaNO3 and NaNO2 (with air or O2) assist the sp3-C−H bond acetoxylation of substrates bearing an Ndirecting group. It has been proposed previously that a redox couple is operative. The role played by NOx anions is examined in this investigation. Evidence for an NOx anion interaction at PdII is presented. Palladacyclic complexes containing NOx anions are competent catalysts for acetoxylation of 8-methylquinoline, with and without exogenous NaNO3. The oxidation of 8-methylquinoline to the corresponding carboxylic acid has also been noted at PdII. 18O-Labeling studies indicate that oxygen derived from nitrate appears in the acetoxylation product, the transfer of which can only occur by interaction of 18O at Pd with a coordinating-acetate ligand. Nitrated organic intermediates are formed under catalytic conditions, which are converted to acetoxylation products, a process that occurs with(50 °C) and without Pd (110 °C). A catalytically competent palladacyclic dimer intermediate has been identified. Head-space analysis measurements show that NO and NO2 gases are formed within minutes on heating catalytic mixtures to 110 °C from room temperature. Measurements by in situ infrared spectroscopy show that N2O is formed in sp3-C−H acetoxylation reactions at 80 °C. Studies confirm that cyclopalladated NO2 complexes are rapidly oxidized to the corresponding NO3 adducts on exposure to NO2(g). The investigation shows that NOx anions act as participating ligands at PdII in aerobic sp3-C−H bond acetoxylation processes and are involved in redox processes.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2017 American Chemical Society. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details. |
Dates: |
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Institution: | The University of York |
Academic Units: | The University of York > Faculty of Sciences (York) > Chemistry (York) |
Funding Information: | Funder Grant number EUROPEAN COMMISSION 115360 |
Depositing User: | Pure (York) |
Date Deposited: | 17 Feb 2017 16:20 |
Last Modified: | 10 Mar 2025 00:05 |
Published Version: | https://doi.org/10.1021/jacs.6b10853 |
Status: | Published |
Refereed: | Yes |
Identification Number: | 10.1021/jacs.6b10853 |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:112522 |
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