Electroreductive synthesis of oligosilanes and polysilanes with ordered sequences

Electrochemical synthesis of symmetrical difunctional disilanes as precursors for organofunctional silanes

“…Although there exist several papers in the literature dealing with the electrochemical formation of methylated or phenylated disilanes [18][19][20][21], much less attempts have been made to reduce chlorosilanes bearing one or more functional groups on the silicon atom. Besides a patent claiming the formation of 1,2-difunctional disilanes by the electrolysis of chlorosilanes R 0 R 2 SiCl (R 0 = Me, Ph, MeO, allyl, octyl) in THF with various supporting electrolytes and two metal electrodes [17], to the best of our knowledge only one publication exists dealing with the electrohemical Si-Si bond formation starting from a functional chlorosilane: the formation of 1,3-dihydrotrisilanes by co-electrolysis of HMe 2 SiCl and Ph 2 SiCl 2 with Mg electrodes in THF/LiClO 4 [19].…”

“…Besides a patent claiming the formation of 1,2-difunctional disilanes by the electrolysis of chlorosilanes R 0 R 2 SiCl (R 0 = Me, Ph, MeO, allyl, octyl) in THF with various supporting electrolytes and two metal electrodes [17], to the best of our knowledge only one publication exists dealing with the electrohemical Si-Si bond formation starting from a functional chlorosilane: the formation of 1,3-dihydrotrisilanes by co-electrolysis of HMe 2 SiCl and Ph 2 SiCl 2 with Mg electrodes in THF/LiClO 4 [19].…”

Electrochemical reduction of alkoxychlorosilanes for Si–Si bond formation

“…These studies, however, have been rather limited to the reduction of alkyl-or aryl-substituted chlorosilanes, and much less is known for those bearing functional groups. A few years ago, Kashimura et al showed that hydrochlorosilanes can be cross-coupled electrochemically with dichloromono-, di-and trisilanes to afford a,xdihydrooligosilanes, respectively [6]. More recently, Grogger et al reported similar synthesis of 1,2-dihydrodisilanes by anodic homo-coupling reactions of chlorohydrosilanes [7].…”

Electroreductive Synthesis of Polysilanes with Ordered Sequences

“…Stepwise synthesis of oligosilanes [22,23] This method is also applicable to the synthesis of trisilanes and tetrasilanes. For example, the electroreductive cross coupling of organodichlorosilanes (3) with chlorotrimethylsilane (1b) (5 equivalent to 3) gave the corresponding trisilanes 4 in moderate to good material yields (Scheme 5) and that of 1,2-dichloro-1,1,2-trimethyl-2-phenyldisilane (5) and 1b (5 equivalent to 5) gave tetrasilane 6 in 55% yield (Scheme 6).…”