title: A computational study of tert-butylbenzenium ions.
abstract: A computational study of tert-butylbenzenium ions has been performed. Structures and energies of the various isomers and the transition states for their interconversions have been determined. The existence of a stable π-electron complex (called A1) between a tert-butyl cation and a benzene molecule has been confirmed. Other minimum points on the potential energy surface corresponding to π-complexes were found, but the barriers for transforming these complexes into the stable π-electron complex A1 are so low that the transformation into the stable structure can take place at all temperatures. The structures were evaluated at the DFT-B3LYP level of theory. The energies were evaluated with the Gaussian-3 (G3B3) and CBS (CBS-QB3) composite methodologies. A discussion of published experimental data in view of the computational results is given. It is pointed out that it should be possible to show the presence of the π-complex by IR spectroscopy. The computations show that the π-complex has a very strong IR band in an otherwise empty region.
authors.affiliation: inGAP Center for Research Based Innovation, Department of Chemistry, University of Oslo, P.O. Box 1033, Blindern, N-0315 Oslo, Norway. stein.kolboe@kjemi.uio.no
authors.forename: Stein
authors.initials: S
authors.lastname: Kolboe
mesh_terms: D001555:Benzene Derivatives / Q000737:chemistry*; D007477:Ions / Q000737:chemistry; D011789:Quantum Theory
chemical_list: D001555:Benzene Derivatives; D007477:Ions; C063841:tert-butylbenzene