Zb. Maksic et al., Protonation of archetypal aromatic and antiaromatic systems - G2 studies of benzene and cyclobutadiene, CHEM PHYS, 253(1), 2000, pp. 59-71
The problem of protonation of benzene (B) and cyclobutadiene (CB) is addres
sed by the ab initio G2 benchmark computations. It appears that the sigma-c
omplexes are the most favourable protonated forms in both cases. The proton
affinity (PA) of (CB) is higher by 45 kcal/mol than that of B, which is ra
tionalized by a decrease in the antiaromatic destabilization of the four-me
mbered ring and stabilization by the allylic cation formation upon protonat
ion accompanied by the ring puckering, which enables an effective additiona
l homoconjugative interaction. The barrier for the hydrogen ring walk in B
is estimated to be 8.6 kcal/mol leading to seven equivalent hydrogens on th
e NMR time scale. In contrast, this barrier in CB is 43.6 kcal/mol implying
that the ring walk is precluded in this cationic system. The ring flipping
inversion barrier of the sigma-protonated CB is estimated to be 7 kcal/mol
thus being in good accordance with experiment. The striking structural fea
tures of sigma and pi-protonated configurations of B and CB involve degrees
of pyramidalization and tetrahedral distortions of carbon atoms, which are
briefly discussed. Some practical models, alternative to the G2 scheme, de
signed for studying the PA of aromatic and antiaromatic compounds are exami
ned and recommended. (C) 2000 Elsevier Science B.V. All rights reserved.