Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 2011-04-14

A computational study of tert-butylbenzenium ions.

Stein Kolboe

Index: J. Phys. Chem. A 115(14) , 3106-15, (2011)

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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.