Univariate Prediction of Hammett Parameters and Select Relative Reaction Rates Using Loewdin Atomic Charges.

Abstract

Loewdin charges from density functional theory calculations were used here to obtain general, univariate linear correlations for the prediction of experimental Hammett parameters and relative reaction rates. While previous studies have established that Hirshfeld and CM5 charges perform strongly as univariate predictors, the near-ubiquitous Loewdin charges have not yet been evaluated. To this end, we assess the predictive capability of Loewdin charges for three chemical systems. First, we show that Loewdin charges outperform Hirshfeld and CM5 charges for Hammett parameter prediction. Second, we see that Loewdin charges generally perform comparably to Hirshfeld charges for predicting the relative rates of olefin cleavage by photoexcited nitroarenes. The single case of poor correlation, between relative rates and the Loewdin charges on nitrogen sites, is ameliorated when considering the net charge on the NO₂ group. Third, we show that Loewdin, Hirshfeld, and CM5 charges all perform very well for generating correlations for relative reaction rates for C-H activation of 9-(4-X-phenyl)-9H-fluorene substrates by a transition metal catalyst. The equations generated throughout the study enable the prediction of Hammett parameters and relative reaction rates. These tools can accelerate synthetic and experimental studies by enabling the in silico prediction of uncharacterized chemical properties.