Imino(silyl)disilenes: application in versatile bond activation, reversible oxidation and thermal isomerization
Richard Holzner, Amelie Porzelt, Uhut S. Karaca, Fiona J. Kiefer, Philipp Frisch, Daniel Wendel, Max C. Holthausen, Shigeyoshi Inoue
Abstract
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.