An NHC‐Mediated Metal‐Free Approach towards an NHC‐Coordinated Endocyclic Disilene

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 Si 10 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.