Non-pentagonal unsaturated dodecahedranes - in-plane delocalized 4C/3e radical cations and sigma-bishomoaromatic 4C/2e dications

An intriguing route from bissecododecahedrenes to 11,17-disubstituted bisho mododecahedrene (7) provides access to X-ray crystallographic data (i.e. py ramidalization angle of ca. 22 degrees). Electrochemical oxidation of the p arent olefin (4, E-pc = 1.46 V) leads via the bishomododecahedradiene (3, d (pi pi) = 3.0 Angstrom, E-1/2 = 0.84 V, E-pc = 1.67 V) to the in-plane delo calized 4C/3e radical cation (3(.+), d(pi pi) = 2.85 Angstrom) and the sigm a-bishomoaromatic 4C/2e dication (3(2+), d(pi pi) = 2.71 Angstrom). (C) 200 0 Elsevier Science Ltd. All rights reserved.