Benchmark Study on the Calculation of ¹¹⁹Sn NMR Chemical Shifts

A new benchmark set termed SnS51 for assessing quantum chemical methods for the computation of ¹¹⁹Sn NMR chemical shifts is presented. It covers 51 unique ¹¹⁹Sn NMR chemical shifts for a selection of 50 tin compounds with diverse bonding motifs and ligands. The experimental reference data are in the spectral range of ±2500 ppm measured in seven different solvents. Fifteen common density functional approximations, two scalar- and one spin-orbit relativistic approach are assessed based on conformer ensembles generated using the CREST/CENSO scheme and state-of-the-art semiempirical (GFN2-xTB), force field (GFN-FF), and composite DFT methods (r²SCAN-3c). Based on the results of this study, the spin-orbit relativistic method combinations of SO-ZORA with PBE0 or revPBE functionals are generally recommended. Both yield mean absolute deviations from experimental data below 100 ppm and excellent linear regression determination coefficients of ≤0.99. If spin-orbit calculations are not affordable, the use of SR-ZORA with B3LYP or X2C with ωB97X or M06 may be considered to obtain qualitative predictions if no severe spin-orbit effects, for example, due to heavy nuclei containing ligands, are expected. An empirical linear scaling correction is demonstrated to be applicable for further improvement, and respective empirical parameters are given. Conformational effects on chemical shifts are studied in detail but are mostly found to be small. However, in specific cases when the ligand sphere differs substantially between conformers, chemical shifts can change by up to several hundred ppm.