Isomerisation and Insertion Chemistry of Imidosilanes Enabled by Reversible Si(IV)/Si(II) Redox Shuttling

Abstract Spontaneous redox shuttling at silicon is very rare, primarily reflecting the thermodynamic challenges associated with reduction processes for lighter p ‐block elements. Here we show that the reactions of boryl‐substituted silylene {PhC( t BuN) 2 }Si{B(NDippCH) 2 } with an organo‐azide proceed through a Si(IV)‐Si(II)‐Si(IV) series of redox processes involving both oxidative and reductive ligand migration steps. Each of the isomeric compounds related through this reaction manifold is isolable (and can be structurally characterised by X‐ray crystallography), with the overall free energy profile being close to thermo‐neutral. Broader studies within group 14 imply that this redox shuttling is unique to silicon and that reductive ligand migration also plays a role in O‐atom insertion chemistry.