Advancing <sup>19</sup>F NMR Prediction of Metal-Fluoride\nComplexes in Solution: Insights from Ab Initio Molecular Dynamics

<sup>19</sup>F NMR\nparameters are versatile probes for studying\nmetal-fluoride complexes. Quantum chemical calculations of <sup>19</sup>F NMR chemical shifts enhance the accuracy and validity of the resonance\nsignal assignments in complex spectra. However, the treatment of solvation\neffects in these calculations remains challenging. In this study,\nwe establish a successful computational protocol using ab initio molecular\ndynamics simulations for the accurate prediction of <sup>19</sup>F\nNMR chemical shifts in square-planar nickel-fluoride complexes. In\nparticular, we have studied in detail the <i>trans</i>-[NiF(2,3,4,5-C<sub>6</sub>F<sub>4</sub>I)(PEt<sub>3</sub>)<sub>2</sub>] complex in a\nbenzene solution. Our computations revealed that accounting for the\ndynamic conformational flexibility of the complex, including intramolecular\ninteractions, is crucial for obtaining reliable <sup>19</sup>F NMR\nchemical shifts. Overall, this study advances the understanding of\nemploying state-of-the-art quantum chemistry methods to accurately\nmodel <sup>19</sup>F NMR chemical shifts of nickel-fluoride complexes,\nemphasizing the importance of addressing solvation effects in such\ncalculations.