Isomerisation and Insertion Chemistry of Imidosilanes Enabled by Reversible Si(IV)/Si(II) Redox Shuttling
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(<sup>t</sup>BuN)<sub>2</sub>}Si{B(NDippCH)<sub>2</sub>} 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.
Authors
- Simon Aldridge (ORCID: https://orcid.org/0000-0001-9998-9434)
- Agamemnon E. Crumpton (ORCID: https://orcid.org/0000-0002-0786-5205)
- Caitilín McManus (ORCID: https://orcid.org/0000-0002-2243-493X)
- Yuwen Wang (ORCID: https://orcid.org/0000-0001-8781-3394)
- Jianqin Tang
Institutions
- University of Oxford (GB)
Publication Details
- Journal
- Angewandte Chemie International Edition
- Published
- 2025-04-23
- DOI
- https://doi.org/10.1002/anie.202505872
- Citations
- 3
- Primary Topic
- Organoboron and organosilicon chemistry
- Type
- article
- Field-Weighted Citation Impact
- 2.81
Funders
- University of Oxford
- Engineering and Physical Sciences Research Council