Gyton, Matthew Robert orcid.org/0000-0002-7565-5154, Royle, Cameron, Beaumont, Simon K. et al. (2 more authors) (2023) Mechanistic Insight into Molecular Crystalline Organometallic Het- erogeneous Catalysis Through Parahydrogen Based Nuclear Mag- netic Resonance Studies. Journal of the American Chemical Society. 2619–2629. ISSN 1520-5126
Abstract
The heterogeneous solid-gas reactions of crystals of [Rh(L2)(propene)][BArF4] (1, L2 = tBu2PCH2CH2PtBu2) with H2 and propene, 1-butene, propyne or 1-butyne are explored by gas-phase NMR spectroscopy under batch conditions at 25oC. The temporal evolution of the resulting Parahydrogen Induced Polarization effects (PHIP) measures catalytic flux, and thus interrogates the efficiency of catalytic pairwise para-H2 transfer, speciation changes in the crystalline catalyst at the molecular level, and allows for high quality single scan 1H, 13C NMR gas-phase spectra for the products to be obtained, as well as 2D-measurements. Complex 1 reacts with H2 to form dimeric [Rh(L2)(H)(μ-H)]2[BArF4]2 (4), as probed using EXAFS; while a single-crystal of 1 equilibrates NMR silent para-H2 with its NMR active ortho isomer, contemporaneously converting to 4, and 1 and 4 each convert para-H2 to ortho-H2 at different rates. Hydrogenation of propene using 1 and para-H2 results in very high initial polarization levels in propane (>85%). Strong PHIP was also detected in the hydrogenation products of 1-butene, propyne and 1-butyne. With propyne a competing cyclot- rimerization deactivation process occurs to afford [Rh(tBu2PCH2CH2PtBu2)(1,3,4-Me3C6H3)][BArF4], while with 1-butyne rapid isom- erization of 1-butyne occurs to give a butadiene complex, which then reacts with H2 slowly to form catalytically active 4. Surprisingly, the high PHIP hydrogenation efficiencies allow hyperpolarisation effects to be seen when H2 is taken directly from a regular cylinder at 25oC. Finally, changing the chelating phosphine to Cy2PCH2CH2PCy2 results in initial high polarization efficiencies for propene hydrogenation but rapid quenching of the catalyst competes to form the zwitterion [Rh(Cy2PCH2CH2PCy2){h6-(CF3)2(C6H3)}BArF3
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2023 The Authors. |
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 EPSRC Calaysis Hub Dec 2021 round EPSRC EP/M024210/2 |
Depositing User: | Pure (York) |
Date Deposited: | 03 Jan 2023 12:30 |
Last Modified: | 21 Jan 2025 18:07 |
Published Version: | https://doi.org/10.1021/jacs.2c12642 |
Status: | Published |
Refereed: | Yes |
Identification Number: | 10.1021/jacs.2c12642 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:194813 |
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Filename: jacs.2c12642.pdf
Description: Mechanistic Insights into Molecular Crystalline Organometallic Heterogeneous Catalysis through Parahydrogen-Based Nuclear Magnetic Resonance Studies
Licence: CC-BY 2.5