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Aromaticity of Diazaborines and Their Protonated Forms
journal contribution
posted on 2016-01-04, 00:00 authored by Milovan Stojanović, Marija Baranac-StojanovićSubstitution of a CH group in benzene
with nitrogen has a little
effect on its aromaticity (Wang et al., Org. Lett. 2010, 12, 4824). How does the same
type of substitution affect aromatic character of the three isomeric
azaborines? Does further protonation change aromaticity of diazaborines?
This work is aimed at answering these questions. Such a knowledge
should be of interest for further exploration and application of BN/CC
isosterism. Aromaticity of diazaborines and their protonated forms
is studied with the aid of four aromaticity indices, HOMA, NICS(0)πzz, PDI and ECRE. Generally, NICS(0)πzz and PDI point to similar aromaticity of diazaborines and their parent
azaborines, while HOMA and ECRE indicate some changes. Thus, aromaticity
of 1,2-azaborine slightly decreases/increases when CH meta/ortho,para to B is substituted
with nitrogen. Aromaticity of the most aromatic 1,3-azaborine remains
almost unchanged when CH meta to B and N is replaced
with nitrogen, and becomes slightly weaker when any other CH group
is substituted with nitrogen. Replacement of the CH ortho to N in 1,4-azaborine does not change much its cyclic delocalization,
while replacement of the CH ortho to B leads to smaller
cyclic delocalization. Protonated forms are either of similar or decreased
aromaticity compared with neutral molecules.