Solvent-Free Access to Lappert´s Heavier Tetrylenes E{N(SiMe3)2}2 (E = Ge, Sn, Pb)

Mechanochemistry is a rapidly emerging synthetic approach that gained momentum in organic synthesis, catalysis, and materials chemistry. Its growing popularity stems from its ability to provide fast and efficient chemical transformations with a reduced environmental footprint as well as enabling products not accessible in solution. However, despite its demonstrated advantages, the number of examples in the realm of main group chemistry is still rare and far between. Herein, iconic Lappert´s heavier tetrylenes E{N(SiMe3)2}2 (E = Ge(1), Sn(2), Pb(3)) have been successfully prepared from GeCl2(1,4-dioxane), SnCl2 or PbCl2 and Li{N(SiMe3)2} via completely solvent-free mechanochemical route and subsequent sublimation. This high-yielding and scalable approach represents a significantly greener improvement over all previously reported procedures.