Halosilanes electrochemical reduction

There is a rich literature on preparative electrochemical reductions of halosilanes. Dessy et al. reported that Ph3SiH was formed by the electrochemical reduction of Ph3SiCl in 1,2 dimethoxyethane (DME) using a dropping mercury cathode at - 3.1 V vs. AgClOJAg [80]. Although the ultraviolet spectra of the solutions after electrolysis were identical with the spectra of an authentic sample of Ph3SiH, the product was not isolated. 

Although the electrochemical reduction of halosilanes exhibits a single irreversible wave (a fast dimerization of the presumed intermediate radical occurs at... 

The electrochemical reduction of halosilanes and germanes in aprotic solvents to give disilanes and digermanes is irreversible and takes place at a low potential. Bu MeCgFsSiCl forms volatile derivatives with alcohols, carboxylic acids, thiols, and amines. All show remarkable hydrolytic stability and are suitable for gas chromatography with electron capture detection. ... 

Although halosilanes undergo smooth nucleophilic substitution at the silicon, they are rather inert to redox reactions. Therefore, chlorosilanes are usually used as trapping agents of anionic intermediates generated by electroreduction of organic compounds. However, in the absence of other reactive substrates halosilanes are reduced electrochemically to form Si-Si bonds. Indeed, there are a number of reports in the literature of the cathodic reduction of chlorosilanes (Sect. 4.2). 

---