The 103Rh NMR spectroscopy and relaxometry of the rhodium formate paddlewheel complex
The 103Rh NMR spectroscopy and relaxometry of the rhodium formate paddlewheel complex
The nuclear magnetic resonance (NMR) spectroscopy of spin-1/2 nuclei with low gyromagnetic ratio is challenging due to the low NMR signal strength. Methodology for the rapid acquisition of 103Rh NMR parameters is demonstrated for the case of the rhodium formate “paddlewheel” complex Rh2(HCO2)4. A scheme is described for enhancing the 103Rh signal strength by polarization transfer from 1H nuclei, which also greatly reduces the interference from ringing artifacts, a common hurdle for the direct observation of low-γ nuclei. The 103Rh relaxation time constants T1 and T2 are measured within 20 min by using 1H-detected experiments. The field dependence of the 103Rh T1 is measured. The high-field relaxation is dominated by the chemical shift anisotropy mechanism. The 103Rh shielding anisotropy is found to be very large: |Δσ| = 9900 ± 540 ppm. This estimate is compared with density functional theory calculations.
Harbor-Collins, Harry
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Sabba, Mohamed
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Moustafa, Gamal
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Legrady, Bonifac
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Soundararajan, Murari
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Leutzsch, Markus
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Levitt, Malcolm H.
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14 September 2023
Harbor-Collins, Harry
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Sabba, Mohamed
bef5e5e8-18b2-43d9-8969-4a9b25bb8691
Moustafa, Gamal
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Legrady, Bonifac
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Soundararajan, Murari
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Leutzsch, Markus
facee439-cca3-43f4-8996-c35d3454dea8
Levitt, Malcolm H.
bcc5a80a-e5c5-4e0e-9a9a-249d036747c3
Harbor-Collins, Harry, Sabba, Mohamed, Moustafa, Gamal, Legrady, Bonifac, Soundararajan, Murari, Leutzsch, Markus and Levitt, Malcolm H.
(2023)
The 103Rh NMR spectroscopy and relaxometry of the rhodium formate paddlewheel complex.
Journal of Chemical Physics, 159 (10), [104307].
(doi:10.1063/5.0165830).
Abstract
The nuclear magnetic resonance (NMR) spectroscopy of spin-1/2 nuclei with low gyromagnetic ratio is challenging due to the low NMR signal strength. Methodology for the rapid acquisition of 103Rh NMR parameters is demonstrated for the case of the rhodium formate “paddlewheel” complex Rh2(HCO2)4. A scheme is described for enhancing the 103Rh signal strength by polarization transfer from 1H nuclei, which also greatly reduces the interference from ringing artifacts, a common hurdle for the direct observation of low-γ nuclei. The 103Rh relaxation time constants T1 and T2 are measured within 20 min by using 1H-detected experiments. The field dependence of the 103Rh T1 is measured. The high-field relaxation is dominated by the chemical shift anisotropy mechanism. The 103Rh shielding anisotropy is found to be very large: |Δσ| = 9900 ± 540 ppm. This estimate is compared with density functional theory calculations.
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104307_1_5.0165830
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More information
Accepted/In Press date: 15 August 2023
e-pub ahead of print date: 12 September 2023
Published date: 14 September 2023
Additional Information:
Funding Information:
We acknowledge funding from the European Research Council (Grant No. 786707-FunMagResBeacons) and EPSRC-UK (Grant Nos. EP/P009980/1, EP/P030491/1, and EP/V055593/1). M.L. acknowledges financial support by the Max-Planck-Gesellschaft and the Max-Planck-Institut für Kohlenforschung. We thank Alexander A. Auer for advice on quantum chemical calculations. We thank Professor Brian E. Mann for advice and historical insights on rhodium NMR. We thank Alexey Kiryutin for sharing his designs for the sample shuttle.
© 2023 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
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Local EPrints ID: 483725
URI: http://eprints.soton.ac.uk/id/eprint/483725
ISSN: 0021-9606
PURE UUID: 28d94fa9-b71a-42d4-8ce5-23eaf8b1d17e
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Date deposited: 03 Nov 2023 18:00
Last modified: 18 Mar 2024 04:06
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Author:
Harry Harbor-Collins
Author:
Mohamed Sabba
Author:
Bonifac Legrady
Author:
Murari Soundararajan
Author:
Markus Leutzsch
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