Paramagnetic ruthenium(III) complex, [(C5Me5)RuCl2]n, is prepared by the reaction of RuCl3·H2O with C5Me5H in refluxing ethanol. Treatment of [Cp*RuCl2]n (Cp* = C5Me5) with cyclic dienes or α,ω-bis(diphenylphosphino)alkanes gives diamagnetic Ru(II) complexes, Cp*RuCl(diene) or Cp*RuCl(dipos), respectively. Cationic diene complex of ruthenium is formed by the reaction of Cp*RuCl(2,5-norbornadiene) with AgBF4.