Electroreduction chlorosilanes

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). 

Summary The electroreductive coupling of chlorosilanes is a relatively new method for the formation of Si-Si bonds [1], Adopting the reaction conditions published by Dunogues and coworkers [2], we developed a special kind of hydrogen anode (Eq. 1) and succeeded in the electrolysis of several chlorosilanes (Eq. 2a, 2b) [3,4],... 

Shono et al. [7] and Yoshida et al. [8] showed in the early 1980s that electroreductive cross coupling is possible in a divided cell with Pt anodes, but no defined anodic oxidation products w reported. In contrast to this, Bordeau et al. electrolyzed different organic substrates with Me2SiCl2 in an undivided cell with sacrificial anodes, thus yielding MgCh as by-product [9]. However, to maintain one of the chloro substituents on the silicon a lai e excess of chlorosilane and the use of an Ni catalyst is unavoidable. Furthermore, HMPA was used as co-solvent. 

The electroreductive coupling of chlorosilanes with mercury electrode has been reported by Hengge in 1976 as a method to form... 

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