J. Chem. Theory Comput. 5, 2239-2247 (2009)


An Ab Initio Study of the Structures and Selected Properties of 1,2-Dihydro-1,2-azaborine and Related Molecules

An ab initio study has been carried out to investigate the effect of replacing [HC−CH]n linkages in benzene by the isoelectronic [HN−BH]n linkages for n = 1, 2, and 3. Such replacements give rise to azaborine, a set of diazaborines, borazine, and pseudoborazine. These replacements lead to significant rearrangements of electron densities in these molecules due primarily to the introduction of the polar B−N bond. As a result, azaborine and diazaborines exhibit much more localized structures than that of benzene. They are also less aromatic than benzene but have a higher degree of aromaticity than borazine. The bonding patterns can be related to the relative stabilities of the diazaborines. Among these molecules, the most stable isomer contains an N−B−N−B linkage, while the two least stable isomers have either a B−B or a N−N bond. Changes in bonding patterns are also reflected in changes in the N1−B2 coupling constant. When N1 and B2 are bonded to the less electronegative atoms C and B, 1J(N1−B2) increases relative to borazine, but when either N1 or B2 is bonded to N, 1J(N1−B2) decreases. Computed NMR chemical shifts and coupling constants are in good agreement with available experimental data.