Electroreductive formation of polysilanes

Abstract

Electroreduction of dichlorosilanes, such as 1 ,I -dichlorodialkylsilanes, I ,2-dichlorotetra-alkyldisilanes, and 1,4-bis(chlorodialkylsilyl)benzenes, with M g electrodes in a single-compartment cell was found to yield the corresponding polysi lanes.We report our new findings that the electroreduction of as 1,l-dichlorosilanes ,I 1,2-dichlorodisilanes,2 and bis(ch1orochlorosilanes with an Mg anode and cathode is effective for silyl)benzenes,3,4 yielded the corresponding polysilanes.1 the formation of Si-Si bonds. The electroreduction of Other metal electrodes were less effective (Pt, Zn, Ni, and trialkylchlorosilanes with Mg electrodes gave disilanes in Cu), The products contained < 2% of the corresponding excellent isolated yields (Scheme 1) , and dichlorosilanes such siloxane.

Electroreductive polymerization of phenylmethyldichlorosilane in a divided cell using a neutral membrane

“…This is a notable difference with the chemical synthesis where bimodal distributions are usually obtained [2]. Molecular weights obtained using a divided cell were higher than those obtained by Hengge [5] and T. Shono [7] using an undivided cell. This is an important contribution in understanding the electroreduction of PhMeSiCl 2 .…”

“…Higher molecular weights of polysilanes were obtained using a resistant anode. Using anodes such as stainless steel, higher molecular weights were obtained than those previously reported [5,7].…”

“…Synthesis by the electrochemical route represents an alternative for the reductive coupling of organodichlorosilanes [5][6][7][8][9][10]. The process takes place in the mixed solvent tetrahydrofuran (THF) + hexamethylphosphoramide (HMPA) and can be schematically represented as follows: …”

Electrochemical synthesis of symmetrical difunctional disilanes as precursors for organofunctional silanes

“…Et 2 N-(Si 2 Me 4 )-NEt 2 and Me 3 SiO-(Si 2 R 4 )-OSiMe 3 can be prepared by coupling Et 2 N-SiMe 2 Cl or Me 3 SiO-SiMe 2 Cl, respectively, with Li in THF [14,15]. Due to our own experience in the electrochemical formation of silyl compounds [16] and based on a Japanese patent [17] we expected the electrochemical coupling of appropriate chlorosilanes to be a reasonable alternative.…”

Electroreductive Synthesis of Polysilanes with Ordered Sequences

“…The use of Mg electrodes was highly effective to the formation of SiSi bond and the synthesis of high molecular weight polysilanes [21,22].…”