The highest absolute values of Pearson correlation coefficient (PCC) were observed in the case of Hirshfeld charges for a benzene ring with a substituent and it generally demonstrates a negative correlation. This trend is valid for TS1 and TS2 as well. Interestingly, PCC in the gas phase for reagent and TS2 is identical and equals -0.74. The same tendency is observed in the condensed phase, yielding PCCs of comparable magnitude for reagent and TS2 (-0.61 and -0.64, respectively). Furthermore, PCCs for TS1 are -0.45 and -0.47 in the gas phase and benzene accordingly. This suggests that the reagent and TS2 are more affected by the nature of the substituents, although the PCC is still low to establish a clear relationship with the effective reaction barrier. We collected Mayer bond orders and bond lengths ( Å) and determined the PCC with the corresponding effective Gibbs free energy values. The correlation is weak for all cases, especially for the bond order with ∆G ‡ eff , for which PCC correlation coefficient is close to zero. The smallest bond orders of R-C 6 H 4 -CNO bond were detected for m-substituted reagents and the shortest bond lengths -for o-substituted reagents. Moreover, the bond order growth was observed in m-F < m-Br < m-Cl < m-MeO < m-CF 3 < m-H < m-NO 2 row, and almost the same row was obtained for bond lengths: o-NO 2 < o-F < o-Cl < o-Br < o-MeO. No other dependencies have been identified. The row of growing bond order is difficult to interpret, whereas the row of growing bond length does not contradict the chemical intuition and corresponds well with ∆G ‡ eff values. Thus, an increase of electron-acceptor properties of the substituent in the o-position slows down the chemical reaction with PCC being -0.85.