Synthesis And Reactivity Of Acyclic Germanimines: Silyl Rearrangement And Cycloadditions

We report the synthesis of aromatic germanimines [(HMDS)(2)Ge=NAr] (Ar = Ph, Mes, Dipp; Mes = 2,4,6-Me3C6H2, Dipp = 2,6-iPr(2)C(6)H(3)) and an investigation into their associated reactivity. [(HMDS)(2)Ge=NPh] decomposes above -30 degrees C, while [(HMDS)(2)Ge=NDipp] engages in an intramolecular reaction at 60 degrees C. [(HMDS)(2)Ge=NMes] was shown to rearrange via a 1,3-silyl migration to give [(HMDS){(SiMe3)-(Mes)N}Ge(NSiMe3)] in a 1:7 equilibrium mixture at room temperature. These latter germanimines react with unsaturated polar substrates such as CO2, ketones, and arylisocyanate via a [2 + 2] cycloaddition pathway.