Theoretical investigation of the formation of the tropylium ion from the toluene radical cation.

The formation of the tropylium ion, C7H7+, in the mass spectrum of toluene is a chemical process that has been extensively studied. There is, however, still debate as to the structure of the moieties and the reaction pathways involved. This work presents the first computationally complete reaction schemes for the formation of tropylium from toluene to be reported. The calculations were performed at the HF/6-31G(d, p) and the DFT/B3LYP/6-311++G(2d) levels of theory using Gaussian 03W. The previously unreported optimized structures and energies for a transition state and an intermediate in one scheme and a transition state in the other have been determined. These results are consistent with the previously reported literature and the available experimental data. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 [ABSTRACT FROM AUTHOR]