Electroreductive Synthesis of Polysilanes, Polygermanes, and Related Polymers with Magnesium Electrodes¹

Abstract

The electroreduction of alkylaryldichlorosilane carried out with Mg cathode and anode in a single compartment cell gave high molecular weight poly(alkylarylsilane) (M(n) = 5200-31000, M(w)/M(n) = 1.4-1.8) in 5-79% yield. The effects of electrode material, monomer concentration, amount of supplied electricity, and ultrasound were investigated. This electroreductive method was also successfully applied to the synthesis of polygermanes, silane-geramane copolymers, and also poly[p-(disilanylene)phenylenes].

Electropolymerization of Polysilanes with Functional Groups

“…The paper 6 briefly introduces the setup of electropolymerization. Here we present the details of the apparatus.…”

“…Aluminum was less effective than Mg, and Cu the worst. It was said that Mg played some important roles in the formation of the Si-Si bond 6 . Although details of the role of Mg in the mechanism of formation of the Si-Si bond are not clear now, the unique reactivity of Mg electrode is undoubtedly shown in this reaction.…”

“…4, the molecular weights of the products became higher with decreasing of the interval time. It could be explained that the alternation of anode and cathode might overcome the difficulty of keeping the electric current at a suitable level due to the increase of the voltage between anode and cathode with progress of the reaction 6 . The maximum voltage was relatively lower at shorter interval time.…”

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].…”

Organic Electrochemical Synthesis Utilizing Mg Electrodes (1) - Facile Reductive Coupling Reactions of Aromatic Halides -

“…We used Mg electrodes for both anode and cathode and utilized alternating electrodes method 10 to minimize the consumption of metal in reaction medium. At first, bromobenzene and benzaldehyde were submitted under our reaction condition, LiClO 4 , 50 V, 350 mA, THF, in order to induce Grignard type reaction (eq.…”