Dehydrogenative Polymerization of New Alkylsilanes Catalyzed by $Cp_2MCl_2$/Red-Al System (M=Ti, Hf): Synthesis of Poly(substituted 3-phenyl-1-silabutanes)

Substituted 3-phenyl-1-silabutanes such as 3-phenyl-1-silabutane (1), 3-(2,5-dimethylphenyl)-1-silabutane (2), 3-(p-chlorotolyl)-1-silabutane (3), and 3-naphthyl-1-silabutane (4) were prepared in 62-96% yield by reduction of the corresponding substituted 3-phenyl-1,1-dichloro-1-silabutanes with LiAlH4. The dehydrogenative polymerization of the monomer silanes was carried out with Cp2MCl2/Red-Al (M=Ti, Hf) catalyst system. The molecular weight of the polymers produced ranged from 700 to 1300 (vs polystyrene) with degree of polymerization (DP) of 5 through 16 and with polydispersity index (PDI)=1.1-2.1. The dehydrogenative polymerization of the monomer silanes with Cp2TiCl2/Red-Al catalyst system occurred at a faster rate and produced somewhat higher molecular weights of polysilane than that with Cp2HfCl2/Red-Al catalyst system.