Semiempirical MO calculations on symmetry governed reactions

Two symmetry governed reactions, the electrocyclic transformation of planar cyclopropyl cation to allyl cation and the dimerization of ethylene to cyclobutane, are examined using a modified INDO method. Results for the cyclopropyl-allyl cation reaction agree well with previously publishedab initio results, and are much improved over previously published CNDO results. The symmetry-allowed disrotatory path is predicted to be significantly favored over the forbidden conrotatory transition. For the ethylene-cyclobutane system two surprising results are predicted within the constraints imposed upon the reaction path: first, that the entire reaction should occur within a small range in the separation of the two ethylene molecules as they approach one another, and second, that the symmetry-forbidden 2 _s +2 _s addition should be slightly favored over the symmetry-allowed 2 _s +2 _a addition. Since the Woodward-Hoffmann rules deal exclusively with changes in electronic energy, it is suggested that they should be applied with some caution to reactions in which changes in nuclear repulsion are quite large during the reaction process.