Novel poly(silylenealkynes), poly(silylenemethylenes), and poly(silyle
nephenylenes) with a regular alternating structure in the polymer back
bone have been prepared by reductive coupling of special substituted s
ilyl triflates or chlorides with potassium-graphite or by ring-opening
polymerization of 1,3-disilacyclobutanes. The functionalization of th
ese polymers with trifluoromethanesulfonic acid and following reaction
s with grignard reagents, amines, or lithium tetrahydridoaluminate gav
e novel polymeric derivatives. The protodesilylation reaction could be
controlled by using different leaving groups (phenyl-, p-tolyl-, or p
-anisyl-groups). in this way, the regular structure of the polymer bac
kbone could be kept during the funtionalization reactions. Novel netwo
rk-polymers have been obtained by intermolecular hydrosilylation react
ions of the modified polymer derivatives. The polymers were characteri
zed by NMR spectroscopy (Si-29, C-13, H-1).