Density-functional B3LYP and ab initio HF calculations are used to study three isomeric systems including: borepin I, boranorbornadiene II, and boranorcaradiene III as well as their X-substituted analogues at two different positions ( X = F, Cl, Br, CH3, OCH3, CF3, CN , and NH2 ). Geometries, enthalpies, and energy barriers for two series of interconversions, IIIX → IX and IIIX → IIX, are calculated using 6-311G* basis set. The B3LYP calculated relative stability is in the order: I (0.00 kcal/mol) > II (23.33 kcal/mol) > III (39.07 kcal/mol). Except for NH2 , the electronic effects of the substituents are generally insignificant on the relative stability. At B3LYP, the gas-phase activation enthalpies for III → I and III → II interconversions are estimated to be very small (0.6 and 0.75 kcal/mol, respectively). The reverse conversions, I → III and II → III, have activation energies of 39.67 and 16.49 kcal/mol, respectively. These energies rule out the possibility of a rapid interconversion of the isomers in the gas phase. Again, none of the substituents, X, can change this situation. Two pathways are proposed for the possible [1, 3]-suprafacial sigmatropic shifts of IIIX → IIX. The partial aromatic characters of planar borepins are estimated using magnetic (NICS) and structural criteria (bond length alternation).