Isolation of an Imino‐N‐heterocyclic Carbene/Germanium(0) Adduct: A Mesoionic Germylene Equivalent

An autoionization of germanium dichloride/dioxane complex with an imino‐N‐heterocyclic carbene ligand ( L ) afforded a novel germyliumylidene ion, [( L )GeCl] + [GeCl 3 ] − , which was fully characterized. Reduction of the germyliumylidene ion with potassium graphite produced a cyclic species [( L )Ge], which can be viewed as both a Ge 0 species and a mesoionic germylene. X‐ray diffraction analysis and computational studies revealed one of the lone pairs on the Ge atom is involved in the π system on the GeC 2 N 2 five‐membered ring. It was also confirmed that the nucleophilic behavior of [( L )Ge] as a two lone‐pair donor.