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

An intriguing route from bissecododecahedrenes to 11,17-disubstituted bishomododecahedrene (7) provides access to X-ray crystallographic data (i.a. pyramidalization angle of ca. 22°). Electrochemical oxidation of the parent olefin (4, Epc=1.46 V) leads via the bishomododecahedradiene (3, dpp=3.0 Å, E1/2=0.84 V, Epc=1.67 V) to the in-plane delocalized 4C/3e radical cation (3·+, dpp=2.85 Å) and the σ-bishomoaromatic 4C/2e dication (32+, dpp=2.71 Å).