Polysilanes with alkoxy groups

Polysilanes with alkoxy groups are more light sensitive than conventional polysilanes. They degrade rapidly in the presence of light in agreement with the facile formation of silylene from dialkoxydisilanes. Properties of these polymers are currently being investigated. 

Similarly, the conversion of the Si-H unit in poly(phenylsilane) into the more reactive Si-Cl and Si-Br functional group can be easily effected by the reaction with carbon tetrachloride and carbon tetrabromide, respectively (Fig. 7.19) [63]. The chlorination or bromination does not affect the Si-Ph substituent but only involves the Si-H bonds. In these reactions about 80% of the Si-H bonds can be converted into the corresponding Si-X bonds. These halogenated polysilanes are reactive polymers that can react with other types of nucleophiles such as alcohols to afford polysilanes containing alkoxy groups [63]. 

The second approach to linear polysilanes is based on the modification of polysilanes prepared by the reductive coupling method. The severe conditions of this reaction allow only alkyl or aryl substituents at the silicon atom in the starting dichlorosilane. Therefore only alkyl or aryl substituted polysilanes are known. We have successfully prepared new polysilanes with pendant alkoxy and amino side groups. This approach allows fine tuning of the properties of... 

The presence of alkali metal during reductive coupling practically prevents the synthesis of polysilanes with groups which can be easily cleaved under basic conditions, such as pendant alkoxy or amino substituents. Polysilanes with pendant functional groups are not known. We have recently discoverd a very efficient method of functionalization of polysilanes. 

Specifically, the chloro and alkoxy groups of multifunctional organosilanes undergo bulk hydrolysis and condensation, forming polysilane networks in an aqueous environment prior to depositing onto the substrate. As a result, the fraction of initial surface silanols that reacts with the functional organosilane is quite small, and the silylation process is usually non-uniform and difficult to control [181]. 

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