Vinyl groups, i.e. 1,2-units of polybutadiene in the presence of various ruthenium complexes at elevated temperatures undergo an effective reaction of dehydrogenative coupling with vinyltrisubstituted silanes to yield silyl substituted units. This is a new type of functionalization of unsaturated polymers. The reaction products are identified by H-1 and C-13 n.m.r, and FTi.r, spectroscopies as well as g.p.c. methods.