Die Reduktion von Azulen mit Natrium zum Kontaktionen‐Tripel [Dinatrium‐(1,1′,6,6′‐Tetrahydro‐6,6′‐bi(azulen)‐1,1′‐diid)–bis (diglyme)] ∞

The Sodium Reduction of Azulene to the Contact‐Ion Triple [Disodium‐(1,1′,6,6′‐Tetrahydro‐6,6′‐bi(azulene)‐1,1′‐diide)–bis(diglyme)] ∞ Colorless air‐sensitive single crystals can be grown from a diglyme solution after the reduction of azulene by a Na‐metal mirror. Structure determination at 150 K reveals a dimer dianion, in which the seven‐membered rings are connected in 6,6′‐positions and doubly diglyme‐solvated Na + counter cations η 5 ‐coordinate to the five‐membered rings. Based on preceding cyclovoltammetric measurements in aprotic azulene solutions as well as on extensive MNDO enthalpy of formation calculations, a proposal is forwarded how possibly the contact ion triple is formed along a microscopic pathway.