Ultraviolet photoelectron and ab initio study of the conformation of some p-Substituted α-Phenylthioacetonitriles
Abstract
The analysis of the He1 photoelectron spectra of some p-substituted α-phenylthioacetonitriles (X-C6H4SCH2CN; X = NO2, Cl, H, CH3, OCH3,NH2) shows evidence, in agreement with ab initio calculations, regarding the preferred conformation around the CC(ring)–S–C dihedral angle, ψ. By preference, ψ assumes large values; that is, the S–CH2CN bond is significantly out of the ring plane. When the electron-releasing capability of X decreases, conformers with smaller ψ values have new features in the spectra. The dependence of the conformer distribution on steric and electronic factors is discussed.