The conversion of 3- and 4-hydroxybenzonitriles (m- and p-cyanophenols) into oxyanions, followed by IR spectra, ab initio and density functional calculations

The conversion of 3- and 4-hydroxybenzonitriles (m- and p-cyanophenols) into oxyanions has been followed by IR spectra, ab initio HF, MP2 6-31G(d) and density functional BLYP, B3LYP 6-31G(d) force field calculations. In a general agreement between theory and experiment, the conversion causes a 34 cm21 frequency decrease in the cyano stretching band, 3.2-fold increase in its integrated intensity and other essential spectral changes in the para-isomer; for the meta-one the corresponding values are 13 cm21 and 2.3-fold, respectively. According to the calculations, both molecule and anion of 4-hydroxybenzonitrile are more stable (due to the polar resonance) than the corresponding meta-substituted species. The strongest structural changes, caused by deprotonation, are the 0.105 A ° shortenings of the Ph–O bonds, 0.054 A ° lengthenings (mean values) of the adjacent CC bonds and essential bond angle changes in the phenylene rings near the oxyanionic centers. In the case of para-isomer these changes are related to the formation of a quasi-para-quinonoidal structure of the phenylene ring in the oxyanion. According to the electronic density analysis, a bit less (Mulliken) or a bit more (natural bond orbital) than halves of the anionic charges remain localized at the oxyanionic centers. Hydrogen bonds have also been discussed. q 2003 Elsevier B.V. All rights reserved