Equilibrium Formation of Stable All-Silicon Versions of 1,3-Cyclobutanediyl

Main group analogues of cyclobutane-1,3-diyls are fascinating due to their unique reactivity and electronic properties. So far only heteronuclear examples have been isolated. Here we report the isolation and characterization of all-silicon 1,3-cyclobutanediyls as stable closed-shell singlet species from the reversible reactions of cyclotrisilene c-Si₃ Tip₄ (Tip=2,4,6-triisopropylphenyl) with the N-heterocyclic silylenes c-[(CR₂ CH₂ )(NtBu)₂ ]Si: (R=H or methyl) with saturated backbones. At elevated temperatures, tetrasilacyclobutenes are obtained from these equilibrium mixtures. The corresponding reaction with the unsaturated N-heterocyclic silylene c-(CH)₂ (NtBu)₂ Si: proceeds directly to the corresponding tetrasilacyclobutene without detection of the assumed 1,3-cyclobutanediyl intermediate.