New complex silicon-containing molecules were made by B(C6F5)3-catalyzed hydrosilation, dehydrocoupling, and dealkylative coupling reactions starting from Si-H reagents. The scope of reactions starting from disilane was expanded to include the formation of silicon-sulfur1, silicon-oxygen and silicon-alkyl side-chains. Reaction inhibition was found with some heteroatom substrates, such as phenols and imines, that strongly bound to B(C6F5)3, and was consistent with the proposed mechanism (Chapter 2). B(C6F5)3 was found to be selective for Si-H activation in reactions of disilane and no competing Si-Si bond cleavage side-reactions were observed. This result will guide future studies and application of B(C6F5)3-catalyzed reactions with polysilanes. A different type of selectivity, the competing B(C6F5)3-catalyzed over-reduction, is evaluated and discussed in Chapter 3. This over-reduction reaction was classified into two distinct cases: alkyl groups for which over-reduction reaction was dependent on the steric bulk of the alkyl group and benzylic groups for which over-reduction was dependent on having an alpha-aryl group. These reactions are consistent with the proposed Piers-Oestreich mechanism (see Chapter 3) and suggest the rate-determining step for over-reduction is the nucleophilic attack of the alkoxysilane (R -O-SiR3) to the R3Si•••H•••B(C6F5)3 complex. Benzylic side-chains were over-reduced regardless of the steric bulk of the aryl groups. Literature precedents suggest that benzyl over-reductions must undergo an alternative mechanism to the Piers-Oestreich mechanism. A number of mechanisms have been proposed in the literature and in Chapter 3, suggesting conventional heteroatom substrate borane or silane-borane complexation. Furthermore, over-reduction of benzylic sulfur containing side-chains was found and this reaction was exploited in the B(C6F5)3-catalyzed synthesis of unique silicon-sulfur silicon-containing products. These over-reduction reactions highlighted the role of the silane for over-reduction and the challenges associated with the post-polymerization modification of poly(phenylsilane). The advances in B(C6F5)3-catalyzed synthesis of small silane molecules suggested reaction conditions and gave spectroscopic benchmarks that were applied to the post polymerization modification of poly(phenylsilane) (Chapter 4). New X-modified poly(phenylsilane) derivatives with thiolato (sulfur), alkoxy/aryloxy (oxygen), amido (nitrogen) and alkyl(carbon) side-chains were prepared with 10-40% incorporation of the ‘X’ group into poly(phenylsilane). These new polysilanes were characterized by the following methods: 1H/13C/29Si NMR, IR, MALS-GPC, EA, and UV-vis absorption spectroscopy. Together, these characterization methods showed that the polysilane had not undergone Si-Si cleavage and thus demonstrated the utility of B(C6F5)3 for the selective activation of Si-H bonds. Thermal decomposition of X-modified poly(phenylsilane) derivatives and parent poly(phenylsilane) showed interesting redistribution pathways (Chapter 5). The thermal decomposition products of poly(phenylsilane) were identified: volatile monosilanes, a structurally complex not-yet-identified phenylsilicon-containing material generated at 500 °C, and a mixture of silicon carbide (SiC) and elemental carbon generated at 800 °C. The B(C6F5)3-catalyzed post-polymerization method (Chapter 4) was evaluated based on the substitution percentage for X-functionalized poly(phenylsilane) derivatives. Reactions of highly electron-donating substrates gave a low amount of X incorporation (10%, e.g. aryloxy side-chains derived from phenol). Aryloxy groups were alternatively introduced via demethanative coupling, which gave a polymer with a greater substitution percentage (25%). The overall impact of the H-to-X substitution reactions was gauged by UV-vis absorption spectra and desirable UV absorption properties would require the modified poly(phenylsilane) to have a high degree of substitution. / Graduate / 2017-09-02