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Updated: Jan 13, 2026

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Combined DFT protocol for the calculation of 31P NMR shifts in platinum complexes
Svetlana A Kondrashova1, Shamil K Latypov1
1Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Kazan, Tatarstan 420088, Russian Federation. lsk@iopc.ru.
None:
In this study, a comparative analysis of calculated and experimental 31P NMR shifts for a wide range of model Pt(0), Pt(II) and Pt(IV) complexes was conducted, and it was observed that, on the whole, the theoretical results reproduced the experimental data well. However, some particularities have to be accounted for phosphorus-containing groups with different donor properties. For example, for σ-donor phosphorus atoms in platinum complexes, 31P NMR shifts can be calculated only within the framework of the fully relativistic matrix Dirac-Kohn-Sham (mDKS) level (RMSE = 4.6 ppm). Alternatively, for π-donating phosphorus, the non-relativistic level may be sufficient, although the accuracy is somewhat low (RMSE = 8.2 ppm). The approach allows for the assignment of challenging structures with several isomerization modes.
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