Treatment of [RuCl2(eta(6)-C6H6)](2) with 1,2-bis(diphenylphosphino)benzene (abbreviation DPB) led to [RuCl-(eta(6)-C6H6)(dpb)]Cl (2). When complex 2 in methanol was heated at 50 degrees C for 13 h, a cationic trinuclear complex [Ru-3(mu(2)-Cl)(3)(mu(3)-Cl)(2)(dpb)(3)]Cl (3a) was obtained in 75% yield with liberation of the benzene ligand. The cationic trinuclear structure was confirmed by X-ray analysis of [Ru3Cl5(dpb)(3)]PF6 (3b). Three ruthenium atoms were linked by three mu(2)-bridging chloride atoms and two face-capped mu(3)-chloride atoms to form a triangular core of Ru-3(mu(2)-Cl)(3)(mu(3)-Cl)(2).