This paper reports the study of the effects of solvent, support electrolyte and the nature of the electrodes on the electroreduction of di-n-hexyldichlorosilane. The work performed involved the use of different types of sacrificial anode (magnesium, aluminium and zinc) and cathode (magnesium, aluminium, zinc, stainless steel, nickel, carbon and palladium) in tetrahydrofuran containing lithium perchlorate (LiClO 4 ). Monomodal poly(di-n-hexyldichlorosilane) was obtained with Al/Al and Mg/Mg electrode pairs, but the polymer yield was about ten times higher with Al/Al (11%) than with Mg/Mg (1%). From the solvents and co-solvents used (tetrahydrofuran, hexamethylphosphorotriamide, acetone, hexane, toluene, 1,1,3,3-tetramethylurea, tris(3,6-dioxaheptyl)amine, 1,2-dimethoxyethane, N,N-dimethylacetamide and dimethylformamide) with LiClO 4 , only the system tetrahydrofuran hexamethylphosphorotriamide, tetrahydrofuran N,N-dimethylacetamide and tetrahydrofuran toluene have given monomodal poly(di-n-hexyldichlorosilane) using an aluminium anode and stainless-steel cathode. Copyright # 2001 John Wiley & Sons, Ltd.KEYWORDS: electroreduction; di-n-hexyldichlorosilane; poly(di-n-hexyldichlorosilane); sacrificial anode; organic media Polyorganosilanes are polymers whose structures are characterized by having silicon atoms connected by covalent bonds. Interest in them by the scientific community is related to the particular properties proceeding from s-electron displacement in the polymer backbone.1±3 So, technological applications of these polymers in electronics, 1,2,4 photocondutive systems 5 and non-linear optics 6 have been developed.Moreover, in the case of polysilenes several applications have been found, in particular as precursors for SiÐC ceramics 7,8 and as photoinitiators for radical polymerization.
