Abstract A convenient metal‐free approach towards an N‐heterocyclic carbene (NHC)‐coordinated disilene 2 is described. Compound 2, featuring the disilene incorporated in cyclopolysilane framework, was obtained in good yield and characterized using NMR spectroscopy and X‐ray crystallography. Density functional theory (DFT) calculations of the reaction mechanism provide a rationale for the observed reactivity and give detailed information on the bonding situation of the base‐stabilized disilene. Compound 2 undergoes thermal or light‐ induced (λ=456 nm) NHC loss, and a dimerization process to give a corresponding dimer with a Si10 skeleton. In order to shed light on the dimerization mechanism, DFT calculations were performed. Moreover, the reactivity of 2 was examined with selected examples of transition metal carbonyl compounds.
