Computational Multinuclear NMR of Platinum Complexes: A Relativistic Four-Component Study

Area of Science:

• Inorganic Chemistry
• Computational Chemistry
• Nuclear Magnetic Resonance Spectroscopy

Background:

• Cisplatin and transplatin are platinum-based anticancer drugs.
• Accurate prediction of NMR chemical shifts is crucial for understanding molecular structure and dynamics.
• Relativistic effects significantly influence the properties of heavy elements like platinum.

Purpose of the Study:

• To optimize the structures of 16 cisplatin and transplatin derivatives.
• To evaluate ¹H, ¹⁵N, and ¹⁹⁵Pt NMR chemical shifts using various computational approaches.
• To establish reliable correlations between calculated and experimental NMR data.

Main Methods:

• Density Functional Theory (DFT) with the dyall.ae2z basis set for structure optimization.
• Nonrelativistic and four-component relativistic quantum chemical calculations for NMR shift evaluation.
• Inclusion of solvent effects and vibrational corrections in the calculations.

Main Results:

• Optimized structures for 16 platinum-based compounds were obtained.
• Calculated NMR chemical shifts showed good agreement with experimental values.
• Relativistic effects were found to be essential for accurate ¹⁹⁵Pt NMR shift prediction.

Conclusions:

• The applied computational methods, including relativistic effects, solvent effects, and vibrational corrections, provide reliable predictions of NMR chemical shifts for cisplatin and transplatin derivatives.
• This approach can be valuable for the design and characterization of new platinum-based anticancer agents.