Neutral bishomoaromatic semibullvalenes.

Isolobal substitution of CH units by boron carbonyl groups (BCO) at C2,6 and C2,8,4,6 in semibullvalene favors the delocalized neutral bishomoaromatic systems substantially. The homoaromaticity is documented by the computed diatropic nucleus independent chemical shifts (NICS). In addition, BCO substitution can result in low-lying triplet and open-shell singlet states. In contrast, substitution at C1,5 more than doubles the related Cope rearrangement barrier. The C2,6 and C2,8,4,6 BCO-substituted barbaralanes, barbaralones, and bullvalenes have substantially reduced barriers.