Abstract: | Novel poly(silylenemethylenes) have been prepared by the ring-opening polymerization of 1,3-disilacyclobutanes followed by a protodesilylation reaction with triflic acid. The silicon–aryl bond cleavage could be controlled by using different leaving groups, for instance phenyl- and para-anisyl substituents. The reactions of the triflate derivatives with organomagnesium compounds, LiAlH4, amines, or alcohols gave functional substituted poly(silylenemethylenes). Hydrosilylation reactions or reductive coupling with potassium–graphite led to organosilicon network–polymers, which may serve as suitable precursors for silicon carbide and Si/C/N-based materials. The structures of the polymers were identified by NMR spectroscopy (29Si, 13C, 1H). © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 725–735, 1998 |