Reductive Deamination of a Diaminogermylene Promoted by an Aluminyl Anion: Isolation of Ge(I), Ge(0) and Ge(‐I) Products
The reaction of the potassium aluminyl K[Al(NON)] ([NON]<sup>2-</sup> = [O(SiMe<sub>2</sub>NDipp)<sub>2</sub>]<sup>2-</sup>, Dipp = 2,6-iPr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>) with the diaminogermylene Ge[N(SiMe<sub>3</sub>)<sub>2</sub>]<sub>2</sub> afforded [K(C<sub>6</sub>H<sub>6</sub>)][Al(NON){(Me<sub>3</sub>Si)<sub>2</sub>NGeGeN(SiMe<sub>3</sub>)<sub>2</sub>}] containing an AlGe<sub>2</sub> ring. Structural and computational analysis confirm an aluminacyclodigermene complex that can be considered as an η<sup>2</sup>-coordinated digermyne at aluminium with Ge(I) centres. This compound is an intermediate on the reduction pathway to K<sub>3</sub>[(Ge<sub>4</sub>){Al(NON)}<sub>2</sub>{N(SiMe<sub>3</sub>)<sub>2</sub>}], which contains a distorted tetrahedral cluster of Ge(-I) centres. Characterisation of the dialumane (NON)Al─Al(NON) from this reaction is indicative of sequential one electron redox processes initiated by the aluminyl anion. Repeating the reaction in methylcyclohexane afforded K<sub>2</sub>[{Al(NON)}<sub>2</sub>(Ge<sub>2</sub>)], containing a formally digermanium(0) unit with an exceptionally long Ge═Ge double bond.
Authors
- J. Robin Fulton (ORCID: https://orcid.org/0000-0002-6370-6452)
- Martyn P. Coles (ORCID: https://orcid.org/0000-0003-3558-271X)
- Andrea O’Reilly (ORCID: https://orcid.org/0000-0001-7070-5004)
- Claire L. McMullin (ORCID: https://orcid.org/0000-0002-4924-2890)
- G. Smith
Institutions
- Victoria University of Wellington (NZ)
- University of Bath (GB)
Publication Details
- Journal
- Angewandte Chemie International Edition
- Published
- 2025-08-12
- DOI
- https://doi.org/10.1002/anie.202512812
- Citations
- 1
- Primary Topic
- Synthesis and characterization of novel inorganic/organometallic compounds
- Type
- article
- Field-Weighted Citation Impact
- 0.54