Cyclic Disilylated and Digermylated Germylenes

Abstract

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.