Abstract: Permethylated linear polysilanes, Me (Me2Si), Me with n= 4-10 and 12, underwent skeletal rearrangement to give branched isomers in almost quantitative yields when treated with a catalytic amount of aluminum chloride in refluxing benzene. From the linear polysilanes with n= 4, 5, and 6,(Me, Si), SiMe,(Me, Si) $ i, and (Me3Si) 3SiSiMesiMe3 were obtained, respectively, as single isomers. The polysilanes with n= 7, 8, and 9 were ...