American Chemical Society, The Journal of Physical Chemistry A, 39(119), p. 10091-10100, 2015
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The electron delocalization in 1,2-azaborine, 1,3-azaborine and 1,4-azaborine is studied using Canonical Molecular Orbital contributions to the Induced Magnetic Field (CMO-IMF) method and Polyelectron Population Analysis (PEPA). Contour maps of the out-of-plane component of the induced magnetic field (Bzind) of the π-system show that the three azaborines, in contrast to borazine, sustain much of benzene's π-aromatic character. Among them, 1,3-azaborine exhibits the strongest π-delocalization, while 1,4-azaborine the weakest. Contour maps of Bzind for individual π orbitals reveal that the differentiation of the magnetic response among the three isomers originates from the π-HOMO orbitals, whose magnetic response is governed by rotational allowed transitions to unoccupied orbitals. The low symmetry of azaborines enable paratropic response from HOMO to unoccupied orbitals excitations, with their magnitude depending on the shape of interacting orbitals. 1,3-azaborine presents negligible paratropic contributions to Bzind from HOMO to unoccupied orbitals transitions, were 1,2- and 1,4-azaborine present substantial paratropic contributions, which lead to reduced diatropic response. Natural Bond Orbital (NBO) analysis employing PEPA shows that only the 1,3-azaborine contains π-electron fully delocalized resonance structures.