Early-Transition-Metal Silicon Compounds and Their Roles in the Synthesis of New Polymeric and Ceramic Materials

The objective of this work was to investigate new transition metal silicon complexes as precursors to ceramic materials, or as catalysts for the synthesis of silicon containing polymers. Precursors to metal silicates were based on complexes of the tri(tert-butoxy)siloxy ligand. Very low temperature, clean routes to silicate materials were discovered. The ceramic materials that were investigated in most detail had the compositions MO24SiO2(M = Ti, Zr, Hf). It was shown that these thermolytic methods could be carried out in solution, and used to apply smooth, thin films of the silicate materials. New transition metal silyl complexes were discovered, and some were used in mechanistic studies to demonstrate a mechanism for the d0 metal-catalyzed dehydrocoupling of silanes to polysilanes. This represents a new polymerization mechanism which shows great promise for the synthesis of new polymers.