The easy control of the electrochemical parameters involved in the int
ensiostatic sacrificial anode technique was applied to the stepwise sy
nthesis of silanylene-2,5-thiophenylene backbones with high selectivit
y and versatility not accessible by purely chemical routes. 2,5-Bis(ch
lorodiorganosilyl)thiophenes and related linear poly[2,5-(silanylene)t
hiophene] oligomers with one to three silicon atoms were synthesized b
y electrochemical reduction of 2,5-dibromo- or 2,5-dichlorothiophene i
n the presence of a diorganodichlorosilane.