Synthesis, functionalization and crosslinking reactions of poly(silylenemethylene)s

Novel poly(silylenemethylene)s 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(silylenemethylene)s. 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 nuclear magnetic resonance spectroscopy (²⁹Si, ¹³C, ¹H). Copyright © 1999 John Wiley & Sons, Ltd.