DFT Approach for Predicting 13C NMR Shifts of Atoms Directly Coordinated to Pt: Scopes and Limitations

In this study, comparative analysis of calculated and experimental ¹³C NMR shifts for a wide range of model platinum complexes showed that, on the whole, the theory reproduces the experimental data well. The chemical shifts of carbon atoms directly bonded to Pt can be calculated well only within the framework of the fully relativistic matrix Dirac-Kohn-Sham (mDKS) level (<i>R</i>² = 0.9973, <i>RMSE</i> = 3.7 ppm); however, for carbon atoms not bonded to metal, a more simple, non-relativistic approach can be used. Effective locally dense basis set schemes were developed for practical applications. The efficiency of the protocol is demonstrated using the example of the isomeric structure determination in case of several possible coordination modes.