Predicting the Molybdenum-95 NMR chemical shift in Mo(0) complexes

Nuclear Magnetic Resonance (NMR) spectroscopy plays a fundamental role in rational drug design, given the sensitivity of the chemical shift to the electronic environment of the metal center. Thus, the present study aims to establish a computational protocol for predicting the ⁹⁵Mo chemical shift in Mo(CO)₃(ETPB)₃ , evaluating the influence of structure and solvent on the description of this property. The complex was selected because experimental structural data (X-ray diffraction) and NMR data for the ⁹⁵Mo chemical shift (δ⁹⁵Mo) areavailable. Initially, the NMR-DKH basis set for the Mo atom was developed. After, the geometry of the Mo(0) complex was optimized at the DFT/def2-SVP and DFT/def2-SVP/IEF-PCM(UFF) levels using eight different density functionals, with dichloromethane as the solvent. The GIAO-PBE/NMR-DKH/IEF-PCM(UFF)//B3LYP/def2-SVP/IEF-PCM(UFF) protocol produced the lowest relative deviation for the δ⁹⁵Mo calculation (RD = 0.17%), adequately describing the property for the complexunder study.