Treatment of [Cp2Ti(SH)(2)] (1; Cp = eta(5)-C5H5) with [(CP*RU)(4)(mu(3)-Cl)(4)] (2; Cp* = eta(5)-C5Me5) in a Ti:Ru ratio of 1:1 afforded the hydrosulfide-bridged titanium-ruthenium heterobimetallic complex [Cp2Ti-(mu(2)-SH)(2)RuClCp*] (3). Complex 3 reacted with an excess of triethylamine to give the early-late heterobimetallic cubane-type sulfide cluster [(CpTi)(2)(Cp*Ru)(2)(mu(3)-S)(4)] (4), With a loss of HCl and cyclopentadiene. An X-ray diffraction study and extended Huckel molecular orbital calculations for the 60e(-) cluster 4 demonstrated that 4 has four Ru-->Ti dative bonds and a weak Ti-Ti interaction. The reaction of 4 with 3 equiv of [Cp2Fe][PF6] afforded the dicationic cubane-type cluster [(CPTi)(2)(CP*RU)(2)(mu(3)-S)(4)] [PF6](2) (5), which contains an additional Ru-Ru bond. In contrast, oxidation of 4 with an excess of HCl at room temperature resulted in the formation of the neutral dichloride cluster [(CpTiCl2)(CpTi)(Cp*RU)(2)(mu(3)-S)(4)] (6) Clusters 5 and 6 were converted into each other by treatment with chloride or hexafluorophosphate anion. Furthermore, substitution of one of the cyclopentadienyl ligands in 6 by a chloride anion took place in boiling 1,2-dichloroethane to give the trichloride cluster [(TiCl3)(CpTi)(Cp*Ru)(2)(mu(3)-S)4] (7) The detailed structures of these oxidized cubane-type clusters 5 2DMF, 6.CH2Cl2 and 7.CH2Cl2 as well as the hydrosulfido-bridged dinuclear complex 3 have also been determined by Xray crystallography. The Ti2RU2S4 cuban-type cores in 5-7 differ considerably in structure from each other, depending upon the ancillary ligands bound to the Ti atoms, although they have a Ru-Ru bond and two Ru-->Ti dative bonds in common.