Modern Valence Bond Description of the Electronic Mechanism of a [1,3] Sigmatropic Rearrangement Linking Bicyclo[3.2.0]hept-2-ene and Bicyclo[2.2.1]hept-2-ene (Norbornene)

摘要

Modern valence bond theory, in its spin-coupled (SC) form, is used to examine the bond-breaking and bond-making processes that take place along the lowest-energy path for a gas-phase [1,3] sigmatropic rearrangement linking bicyclo[3.2.0]hept-2-ene and bicyclo[2.2.1]hept-2-ene (norbornene). The changes within the SC wave functions depicting the direct "suprafacial with inversion" pathway reveal in a very clear cut way the singlet diradical character of structures along the plateau in the energy profile.