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Updated: Jul 4, 2025
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Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
2.8K
Structure and bonding in rhodium coordination compounds: a 103Rh solid-state NMR and relativistic DFT study
Sean T Holmes1,2, Jasmin Schönzart1,2, Adam B Philips3
1Department of Chemistry & Biochemistry, Florida State University Tallahassee FL 32306 USA rschurko@fsu.edu.
Chemical Science
|February 9, 2024
Summary
This study introduces advanced 103Rh solid-state NMR methods for analyzing inorganic compounds. These techniques correlate 103Rh chemical shift tensors with molecular structure and bonding.
Area of Science:
- Solid-state NMR Spectroscopy
- Inorganic Chemistry
- Organometallic Chemistry
Background:
- 103Rh is a challenging NMR nuclide with limited existing literature.
- Understanding Rh-ligand bonding and molecular structure is crucial in coordination chemistry.
Purpose of the Study:
- To develop and demonstrate robust 103Rh solid-state NMR (SSNMR) protocols.
- To correlate 103Rh chemical shift tensors with molecular structure and Rh-ligand bonding using DFT calculations.
- To establish a foundation for investigating platinum group elements using these methods.
Main Methods:
- Application of 103Rh SSNMR spectroscopy on stationary samples.
- Utilized broadband adiabatic inversion-cross polarization (BRAIN-CP) and wideband uniform-rate smooth-truncation (WURST) pulse sequences.
- Combined experimental NMR data with relativistic density functional theory (DFT) calculations, including natural bond orbital (NBO) and natural localized molecular orbital (NLMO) analyses.
Main Results:
- Acquisition of 103Rh SSNMR spectra with unprecedented signal-to-noise and uniformity.
- Determination of 103Rh chemical shift tensors.
- Analysis of orbital contributions to magnetic shielding tensors, linking them to structure and bonding.
Conclusions:
- Developed effective 103Rh SSNMR protocols for challenging samples.
- Established correlations between 103Rh chemical shift tensors, molecular structure, and bonding.
- Highlighted the potential of these combined experimental and theoretical methods for broader applications in platinum group element research.
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