Study of the influence of stereoelectronic interactions on the vibrational frequencies of a series of peroxy fluorocarbooxygenated compounds

Stereoelectronic effects were investigated in a series of peroxy fluorocarbooxygenated compounds, using experimental infrared data, theoretical calculations and NBO analysis. The influence of inductive, anomeric and mesomeric interactions over the C O and O O stretching vibrations were evaluated for all the molecules. The carbonylic stretching mode is mainly affected by the inductive interaction, while the lone pair delocalization LpO → σ O C ∗ shows a stronger influence on the O O stretching vibrations. The mesomeric interaction is relevant in determining the planar geometry of the XC(O)O group around the Csp 2 atom.