MNDO Parameters for the Prediction of¹⁹F NMR Chemical Shifts in Biologically Relevant Compounds

Abstract

The semiempirical MNDO methodology for qualitative description NMR chemical shifts has now been extended with the addition of NMR-specific parameters for the fluorine atom. This approach can be employed using semiempirical (AM1/PM3) geometries with good accuracy and can be executed at a fraction of the cost of ab initio and DFT methods, providing an attractive option for the computational studies of (19)F NMR for much larger systems. The data set used in the parametrization is large and diverse and specifically geared toward biologically relevant compounds. The new parameters are applicable to fluorine atoms involved in carbon-fluorine bonds. These parameters yield results comparable to NMR calculations performed at the DFT (B3LYP) level using the 6-31++G(d,p) basis set. The average R (2) and rms error for this data set is 0.94 and 13.85 ppm, respectively, compared to 0.96 and 10.45 ppm when DFT methods are used.