The ring opening of the Dewar form of 1,2-dihydro-1,2-azaborine, 2-aza-3-borabicyclo[2.2.0]hex-5-ene (3) is investigated by theoretical methods by using multiconfiguration SCF (CASSCF) and coupled cluster theory [CCSD(T)] with basis sets up to polarised quadruple-zeta quality. The title compound was previously reported to form photochemically in cryogenic noble gas matrices from 1,2-dihydro-1,2-azaborine (4). Four reaction paths for the thermal ring opening of 3 to 4 could be identified. These are the conventional disrotatory and conrotatory electrocyclic ring-opening pathways where the BN unit is only a bystander. Two more favourable paths are stepwise and involve 1,3-boron-carbon interactions. The lowest energy barrier for the isomerisation reaction, 22 kcal mol(-1), should be high enough for an experimental observation in solution. However, in solution the dimerisation of 3 is computed to have a very low barrier (3 kcal mol(-1)), and thus 3 is expected to be a short-lived reactive intermediate.
Keywords: BN aromatics; Dewar isomer; ab initio; azaborine; reaction mechanism.