For 1-Pr, both 1 H and Si calculated pNMR results show discrepancies compared to the experimental solution values when employing bis-THF structures (see Supporting Information Table ). Using the XRD structure (optimized structure) for 1 H gives shifts of ca. -14.5 and ca. -1.9 ppm (ca. -4.4 and ca. -0.5 ppm) for the "inplane"/group 1 and "out-of-plane"/group 2 signals, respectively, compared to the experimental values of 7.9 and -8.1 ppm, respectively. By removing one THF ligand and maintaining the "in-plane"/"out-of-plane" averaging, the calculations give chemical shifts of ca. 11.0 and ca. -8.0 ppm, or ca. 7.6 and ca. -6.2 ppm when removing the second THF ligand (see Supporting Information Table ). Hence, the models with some THF lost better align with the experimental data. Similarly, for solution Si pNMR "in-plane"/group 1 resonances (group 2 not observed; now considering only 𝛿 vdH-S para ), the XRD structure (optimized structure) gives a shift of -40.9 ppm (optimized structure: -15.0 ppm), deviating substantially from the experimental value of 10.2 ppm. The shifts for Pr(THF)1 and Pr(THF)0 are 24.0 ppm and 16.0 ppm, respectively; here, the Pr(THF)0 model is in better agreement with the experimental data (see Supporting Information Table ). Using the second averaging method, the pNMR shifts are predicted adequately using a Pr(THF)0 model (see Supporting Information Table ), or using a Pr(THF)1 model with the third averaging method (see Supporting Information Table ), but in both cases the calculated parameters are not as close to experiment as for the "in-plane"/"out-of-plane" averaging approach.