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] = [O(SiMeNDipp)], Dipp = 2,6-iPrCH) with the diaminogermylene Ge[N(SiMe)] afforded [K(CH)][Al(NON){(MeSi)NGeGeN(SiMe)}] containing an AlGe ring. Structural and computational analysis confirm an aluminacyclodigermene complex that can be considered as an η-coordinated digermyne at aluminium with Ge(I) centres. This compound is an intermediate on the reduction pathway to K[(Ge){Al(NON)}{N(SiMe)}], 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[{Al(NON)}(Ge)], containing a formally digermanium(0) unit with an exceptionally long Ge═Ge double bond.