Experimental and theoretical vibrational study of isatin, its 5-(NO2, F, Cl, Br, I, CH3) analogues and the isatinato anion

Effects of 5-R substitution (R = NO2, F, Cl, Br, I, CH3) and N-deprotonatio n on the 4000-400 cm(-1) region of the low temperature FT IR spectrum and t he molecular structure of solid isatin are investigated. Harmonic IR spectr a and molecular geometries of the 5-R isatins (except for Br and I analogue s) are calculated at the HF/6-31G(d, p) level and compared with the experim ental solid-state data. In general, substitution has small effect on the mo lecular structure and the IR spectrum of isatin. The nu (CO) triplet in the IR spectra of isatin and its 5-substituted analogues is resulted by vibrat ional splitting of the out-of-phase CO stretching, nu (op)[(CO)(2)]. While the frequency of the nu (op)[(CO)(2)] mode is relatively less affected by 5 -substitution and mainly depends on the substituent mass, the frequency of the in-phase stretching, v(ip)[(CO)(2)], is strongly sensitive to both mass and electronic properties of the substituent. Substitution at C5 has relat ively greater influence on the electron density and the force constant of t he amide than on the ketone carbonyl group. Strong electron-donors shorten and stabilize the unusually long alpha -dicarbonyl CC bond, while electron- accepting groups tend to stretch this bond further. N-Deprotonation brings to elongation of the five membered-ring along the N-C-CO(ketone) vector and expansion of the bonds within the alpha -dicarbonyl part. Theoretical nu ( CO) frequency of isatin is lowered for about 180 cm(-1) upon conversion int o isatinato ion. Harmonic vibrational analysis reveals that only the highes t-frequency nu (CO) mode of the isolated isatinato anion can be considered good group vibration for empirical assignments in spectra of solid isatinat es. Owing to the solid-state influences on the nu[(CO)(2)] modes, no reliab le spectra-structure correlations could be established from the present exp erimental spectroscopic data. (C) 2001 Elsevier Science B.V. All rights res erved.