Synthesis and Reactivity of a Neutral Homocyclic Silylene

Isolation of the neutral homocyclic silylene 2 is possible via amine ligand abstraction with potassium graphite (KC(8)) and subsequent reaction with SiMe(3)Cl from a bicyclic silicon(I) amide J. This reaction proceeds via an anionic homoaromatic silicon ring compound 1 as an intermediate. The twofold‐coordinated silicon atom in the homocyclic silylene 2 is stabilized by an allyl‐type π‐electron delocalization. 2 reacts in an oxidative addition with two equivalents of MeOH and in cycloadditions with ethene, phenylacetylene, diphenylacetylene and with 2,3‐dimethyl‐1,3‐butadiene to afford novel functionalized ring compounds.