A reactive Si4 cage: K(SitBu3)3Si4

KR∗₃Si₄, 2, (R∗ = SitBu₃), formed by the reaction of R∗₄Si₄ with 2 KC₈, is an orange red solid stable at r.t. but decomposes in solution into R∗₄Si₄ and a compound that reacts with excess Me₃SiCl to form (Me₃Si)₄R∗₃ClSi₈. Compound 2 is very sensitive to air and moisture. Its alcoholysis does not stabilize the protonated species HR∗₃Si₄ and ends up in R∗₃Si₃H₃. Compound 2 reacts with 1/2 equivalent ICl to form a violet solid R∗₆Si₈. A 1:1 reaction of 2 with SiBr₄ runs differently to form ditetrahedranyl, R∗₃Si₄-Si₄R∗₃ which is stable at r.t. but transforms into its violet isomer R∗₆Si₈ at higher temperatures. Compound 2 crystallizes as R∗₃Si₄K(18-crown-6) and its crystal structure shows a Si₄-cage with a short Si-K linkage. It opens up at higher temperatures to acquire a unique structure in which a -CH₂-CH₂- group detaches itself from an ether to insert into Si-Si linkage of Si₄-unit to form a bicyclic ring. The residual chain (CH₂)₁₀O₆ closes itself on to a Si atom to form R∗₃Si₃(CH₂-CH₂)Si(C₁₀H₂₀O₆)K(18-C-6).