Theoretical study on the aromaticity of transition states in pericyclic reactions

The aromaticity of transition states in pericyclic reactions such as electrocyclic reactions, cycloaddition reactions, and sigmatropic shifts was studied by the IDA (index of deviation from aromaticity) on the basis of a CASSCF wave function. The aromaticity defined by the IDA classified the allowed and forbidden transition states of pericyclic reactions treated here. The order of the aromaticity levels corresponds to that of the energy barriers of some reactions. The difference between the aromaticity defined by the IDA and that by the magnetic properties as a NICS is also discussed.