Polycondensation vs. cyclization of divinylsubstituted silicon compounds catalyzed by transition metal complexes

In the presence of ruthenium complexes divinyldiorganosilicon compounds undergo de‐ethenated coupling polycondensation yielding under optimum conditions trans‐tactic polysilylene(siloxylene, silazanylene)vinylenes and poly(silylene‐arylene‐vinylenes). Rhodium‐ ([RhX(cod)]₂ X = Cl, OSiMe₃) catalyzed ring closure of oligomeric (dimeric, trimeric) products of intermolecular condensation opens a new route to synthesizing organosilicon exo‐cyclic methylenes. In the presence of Ru‐complexes the cross‐coupling (poly)condensation of di‐ and trivinylsilicon monomers with organic dienes allows syntheses of a series of linear and dendrimeric poly(arylene‐silylene‐vinylene)s.