Electron-withdrawing effect of α-substituents in acyl nitrates on the polarization of the $\mathrm{O\text{-}NO_2}$ bond

Regularities in the Raman ($\mathrm{v_{NO_2}^s}$) and $\mathrm{^{14}N}$ NMR spectra of acetyl nitrates containing various electron-withdrawing $\alpha$-substituents were established by quantum chemical calculations. The experimental data on (poly)-$\alpha$-haloacetyl nitrates (in solutions) revealed no reliable relationship between the halogen nature/number and the spectral characteristics, whereas the computed values of $\delta_N$ and $\mathrm{O\text{-}NO_2}$ bond lengths disclose the substituent effect on the polarization of $\mathrm{O\text{-}N}$ bond and hence on the nitrating power of acyl nitrates.