Two novel disilenes of type ABSi[double bond, length as m-dash]SiAB bearing N-heterocyclic imino (A = NItBu) and trialkylsilyl (B = SitBu31, B = SitBu2Me 2) groups are reported. The reduced steric demand in 2 results in a highly stable, nonetheless flexible system, wherefore (E/Z) isomerization is observed from room temperature up to 90 °C. The proposed isomerization mechanism proceeds via monomeric silylenes in line with experimental results. Despite enhanced stability, disilene 2 retains high reactivity in the activation of small molecules, including H2. The rare example of a disilene radical cation 7 is isolated and shows reversible redox behavior. White phosphorous (P4) selectively reacts with 2 to give the unique cage-compound 8. Selective thermal rearrangement of 2 at higher temperatures yields the A2Si[double bond, length as m-dash]SiB2-type disilene 9 (A = NItBu, B = SitBu2Me), which bears characteristics of a zwitterionic and a dative central Si-Si bond. The proposed mechanism proceeds via an initial NHI migration followed by silyl migration.
