For the first time, olefin cross metathesis has been developed for vinylgermanium compounds. This paper also marks the first case of transition metal‐catalyzed functionalization of heterosilsesquioxanes, which in our case are cubic vinylgermasilsesquioxanes and newly synthesized di(vinylgermyl)substituted double‐decker silsesquioxane. These processes lead to a series of new molecular, unsaturated mono‐ and divinyl‐substituted germasilsesquioxanes, which can be potentially applied as precursors for optoelectronics and for the synthesis of new advanced materials. Additionally, preliminary tests of metathetic copolymerization of divinylsubstituted double‐decker digermasilsesquioxanes (DDSQ‐2ViGe) with selected diolefins proved to be very promising and resulted in the synthesis of novel stereoregular trans‐germasilsesquioxyl‐vinylene‐phenylene macromolecular derivatives. All newly obtained compounds were isolated and characterized by mass and spectroscopic methods.
