The reaction of Cp(2)Co with p-TolSbCl(2) in THF gives (p-TolSb)(n) and [Cp(2)Co][p-TolSbCl(3)]. H-1 NMR experiments show that this method is also useful for the syntheses of the rings (ArSb)(n) (Ar = Ph, o-Tol, m-Tol, p-Tol). The structure of [Cp(2)Co][p-TolSbCl(3)] has been determined by single crystal X-ray diffraction. It contains a centrosymmetric double chlorine-bridged dimeric anion. The two-electron reduction of p-TolSbCl(2) gives (p-TolSb)(n).