Monoreduced 1,2‐dihydrocorannulene versus the parent corannulene

The monoanion of dihydrogenated corannulene isolated in the form of its potassium salt, namely tris(diglyme‐κ³O,O′,O′′)potassium hexacyclo11.5.2.0^4,17.0^7,16.0^10,15.0^14,18]icosa‐1,3,5,7(16),8,10(15),11,13,17‐nonaenide, K(C₆H₁₄O₃)₃](C₂₀H₁₂), has been structurally characterized for the first time. The X‐ray study confirms the previous NMR spectroscopic prediction that the two H atoms are attached to the same six‐membered ring to form 1,2‐dihydrocorannulene, thus destroying the aromaticity of only one arene ring of the corannulene core. The direct comparison of (C₂₀H₁₂)^? with the parent corannulene anion, (C₂₀H₁₀)^?, is provided to illustrate the geometry perturbations caused by rim hydrogenation.