Cyclic Disilylated and Digermylated Germylenes

The preparation of triethylphosphine adducts of cyclic disilylated or digermylated germylenes was achieved by reaction of 1,4-dipotassio-1,1,4,4-tetrakis­(trimethylsilyl)­tetramethyltetrasilane with GeBr2·(dioxane) and PEt3. Phosphine abstraction with B­(C6F5)3 allowed formation of the base-free germylenes, which undergo 1,2-trimethylsilyl shifts to the germylene atom to form the respective silagermene or digermene, which further dimerize in [2 + 2] cycloadditions to tricyclic compounds. The reasons responsible for the germylenes’ completely different reactivities in comparison to the previously studied analogous stannylenes and plumbylenes were elucidated in a theoretical study.