Pt(0) complexes have been widely used as catalysts for important reactions, such as the hydrosilylation of olefins. In this context, nuclear magnetic resonance (NMR) spectroscopy plays an important role in characterising of new structures and elucidating reaction mechanisms. In particular, the Pt-195 NMR is fundamental, as it is very sensitive to the ligand type and the oxidation state of the metal. In the present study, quantum mechanics computational schemes are proposed for the theoretical prediction of the Pt-195 NMR chemical shift and 1J(195Pt–31P) in Pt(0) complexes. The protocols were constructed using the B3LYP/LANL2DZ/def2-SVP/IEF-PCM(UFF) level for geometry optimization and the GIAO-PBE/NMR-DKH/IEF-PCM(UFF) level for NMR calculation. The NMR fundamental quantities were then scaled by empirical procedures using linear correlations. For a set of 30 Pt(0) complexes, the results showed a mean absolute deviation (MAD) and mean relative deviation (MRD) of only 107 ppm and 2.3%, respectively, for the Pt-195 NMR chemical shift. When the coupling constant is taken into account, the MAD and MRD for a set of 33 coupling constants in 26 Pt(0) complexes were of 127 Hz and 3.3%, respectively. In addition, the models were validated for a group of 17 Pt(0) complexes not included in the original group that had MAD/MRD of 92 ppm/1.7% for the Pt-195 NMR chemical shift and 146 Hz/3.6% for the 1J(195Pt–31P).

Nuclear magnetic resonance (NMR) spectroscopy has played an important role in the discovery and design of new drugs with antitumor potential and the Pt-195 NMR has a fundamental role since the Pt-195 nucleus is very sensitive to the nature of the ligands in the coordination sphere and the oxidation state of the metal. The theoretical prediction of the Pt-195 NMR chemical shift is an extremely difficult task in which several factors must be taken into accounts, such as basis sets, electronic correlation, solvent, and relativistic effects. In an earlier study, Paschoal et al. developed the NMR-DKH basis sets and a nonrelativistic protocol for predicting the Pt-195 NMR chemical shift. The authors studied a set of 258 Pt(II) complexes and obtained a mean absolute deviation (MAD) of 168 ppm and a mean relative deviation (MRD) of 5%. However, relativistic calculations with the NMR-DKH basis sets have not been performed. Thus, the present work aims to apply the NMR-DKH in predicting the Pt-195 NMR chemical shift including the relativistic effects. The cisplatin was used as a model and its geometry was optimized and characterized as a minimum point on the potential energy surface at the B3LYP/LANL2DZ/def2-SVP/COSMO level. The Pt-195 NMR chemical shift was calculated at the DFT-Functional-DKFull/NMR-DKH/COSMO, where the functionals BP86, PBE, BLYP, PBE0, and B3LYP were tested. All calculations were carried out in NWCHEM 7.0.0 program. From the calculated results, it can be observed that the pure GGA functionals showing a better performance when compared to the hybrid functional. The best result was obtained at the BLYP-DKFull/NMR-DKH/COSMO level, where a DAM and DRM of only 34 ppm and 1.6% was found.