Reductive Deamination of a Diaminogermylene Promoted by an Aluminyl Anion: Isolation of Ge(I), Ge(0) and Ge(‐I) Products

Abstract The reaction of the potassium aluminyl K[Al(NON)] ([NON] 2− = [O(SiMe 2 NDipp) 2 ] 2− , Dipp = 2,6‐ i Pr 2 C 6 H 3 ) with the diaminogermylene Ge[N(SiMe 3 ) 2 ] 2 afforded [K(C 6 H 6 )][Al(NON){(Me 3 Si) 2 NGeGeN(SiMe 3 ) 2 }] containing an AlGe 2 ring. Structural and computational analysis confirm an aluminacyclodigermene complex that can be considered as an η 2 ‐coordinated digermyne at aluminium with Ge(I) centres. This compound is an intermediate on the reduction pathway to K 3 [(Ge 4 ){Al(NON)} 2 {N(SiMe 3 ) 2 }], 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 2 [{Al(NON)} 2 (Ge 2 )], containing a formally digermanium(0) unit with an exceptionally long Ge═Ge double bond.