Townrow, Oliver P.E., Duckett, Simon B. orcid.org/0000-0002-9788-6615, Weller, Andrew S. orcid.org/0000-0003-1646-8081 et al. (1 more author) (2022) Zintl cluster supported low coordinate Rh(i) centers for catalytic H/D exchange between H2 and D2. Chemical Science. pp. 7626-7633. ISSN 2041-6539
Abstract
Ligand exchange reactions of [Rh(COD){η4-Ge9(Hyp)3}] with L-type nucleophiles such as PMe3, PPh3, IMe4 (IMe4 = 1,3,4,5-tetramethylimidazol-2-ylidene) or [W(Cp)2H2] result in the displacement of the COD ligand to afford clusters with coordinatively unsaturated trigonal pyramidal rhodium(i) centers [Rh(L){η3-Ge9(Hyp)3}]. These species can be readily protonated allowing access to cationic rhodium-hydride complexes, e.g. [RhH(PPh3){η3-Ge9(Hyp)3}]+. These clusters act as catalysts in H/D exchange between H2 and D2 and alkene isomerisation, thereby illustrating that metal-functionalized Zintl clusters are active in both H-H and C-H bond activation processes. The mechanism of H/D exchange was probed using parahydrogen induced polarization experiments.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | Funding Information: We thank Shell Global Solutions International B.V., the University of Oxford and the EPSRC for financial support of this research (Industrial CASE studentship O. P. E. T.; EP/M024210 ASW). The University of Oxford is also acknowledged for access to Chemical Crystallography facilities. Publisher Copyright: © 2022 The Royal Society of Chemistry |
Dates: |
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Institution: | The University of York |
Academic Units: | The University of York > Faculty of Sciences (York) > Chemistry (York) |
Depositing User: | Pure (York) |
Date Deposited: | 15 Jul 2022 08:30 |
Last Modified: | 21 Jan 2025 18:03 |
Published Version: | https://doi.org/10.1039/d2sc02552c |
Status: | Published |
Refereed: | Yes |
Identification Number: | 10.1039/d2sc02552c |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:189110 |
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Description: Zintl cluster supported low coordinate Rh(I) centers for catalytic H/D exchange between H2 and D2
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