A neutral crystalline imino-substituted silyl radical.

The neutral three-coordinated imino(silyl)silyl radical was isolated from the reaction of N-heterocyclic iminosilicon tribromide (IBuN-SiBr) with NaSiBuMe. The radical was fully characterized by X-ray crystallography and electron paramagnetic resonance spectroscopy and supported by quantum chemical calculations.

Imino(silyl)disilenes: application in versatile bond activation, reversible oxidation and thermal isomerization.

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.