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Density-functional computation of 99Ru NMR parameters

Buhl1, Gaemers, Elsevier

  • 1Organisch-chemisches Institut, Universitat Zurich, Switzerland. buehl@mpi-muelheim.mpg.de

Chemistry (Weinheim an Der Bergstrasse, Germany)
|September 26, 2000
PubMed
Summary

Density-functional theory accurately predicts ruthenium-99 chemical shifts and electric field gradients. Hybrid functionals like B3LYP better capture substituent effects and NMR trends than pure functionals.

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Area of Science:

  • Computational Chemistry
  • Quantum Chemistry
  • Nuclear Magnetic Resonance Spectroscopy

Background:

  • Accurate prediction of nuclear magnetic resonance (NMR) parameters is crucial for understanding chemical structure and bonding.
  • Density-functional theory (DFT) offers a computationally efficient approach to calculating molecular properties, including NMR chemical shifts and electric field gradients (EFGs).
  • Previous studies have explored DFT for various transition metal complexes, but systematic evaluation for ruthenium-99 (99Ru) NMR parameters is less common.

Purpose of the Study:

  • To compute 99Ru chemical shifts and EFGs for a diverse set of ruthenium compounds using DFT.
  • To evaluate the performance of gradient-corrected (e.g., BPW91) and hybrid (e.g., B3LYP) DFT functionals in reproducing experimental 99Ru NMR data.
  • To investigate the correlation between computed EFGs and experimental 99Ru NMR linewidths, particularly concerning the influence of molecular geometry.

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Main Methods:

  • Calculations employed gradient-corrected and hybrid variants of DFT.
  • Optimized geometries and 99Ru chemical shifts (δ(99Ru)) were computed for a series of ruthenium complexes.
  • Electric field gradients (EFGs) at the Ru nucleus were calculated and compared with experimental 99Ru NMR linewidths.

Main Results:

  • The B3LYP hybrid functional provided a good description of substituent effects on δ(99Ru), outperforming the BPW91 pure functional.
  • B3LYP qualitatively reproduced empirical trends in EFGs at the Ru nucleus.
  • Computed EFGs for the [Ru(CO)2(iPr-DAB)XY] series correlated well with observed 99Ru NMR linewidths, supporting a quadrupolar relaxation mechanism.
  • Optimized geometries yielded better correlation between calculated EFGs and experimental linewidths than X-ray-derived geometries for the [Ru(CO)2(iPr-DAB)XY] series.

Conclusions:

  • Hybrid DFT functionals, specifically B3LYP, are well-suited for accurately predicting 99Ru chemical shifts and EFGs.
  • Computed EFGs correlate with experimental NMR linewidths, providing insights into relaxation mechanisms in ruthenium complexes.
  • The use of optimized geometries in DFT calculations is recommended for improving the prediction of NMR parameters sensitive to subtle structural variations.