Synthesis and Reactivity of Acyclic Germanimines: Silyl Rearrangement and Cycloadditions

Abstract

We report the synthesis of aromatic germanimines [(HMDS)2Ge═NAr] (Ar = Ph, Mes, Dipp; Mes = 2,4,6-Me3C6H2, Dipp = 2,6-iPr2C6H3) and an investigation into their associated reactivity. [(HMDS)2Ge═NPh] decomposes above -30 °C, while [(HMDS)2Ge═NDipp] engages in an intramolecular reaction at 60 °C. [(HMDS)2Ge═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.