Combined DFT protocol for the calculation of 31P NMR shifts in platinum complexes

Abstract

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.