Access to diverse germylenes and a six-membered dialane with a flexible β-diketiminate.

A nacnac-based tridentate ligand containing a picolyl group (L) was employed to isolate chlorogermylene (1). The reaction of 1 with another equivalent of GeCl2·dioxane surprisingly gave pyridylpyrrolide-based chlorogermylene (2) via C-N bond cleavage and C-C coupling, while with AlCl3, it afforded a transmetalated product, 4. The reaction of L with AlH3·NMe2Et led to an unusual cyclohexane type six-membered dialane heterocycle (5).