The interactions of the benzothiazolate complex, CpCr(CO)(2)(SCSN(C6H4)) (2), and the tetrazole thiolate complex, CpCr(CO)(3)(eta(1)-SCN4Ph) (3), with controlled amounts of Me3OBF4 and (MeO)(2)SO2, respectively, produced the corresponding mu(3)-oxo trinuclear thionate-bridged complexes, [Cp3Cr3(mu(2)-OH)(mu(3)-O)(mu(2)-eta(2)-SCSN(C6H4))(2)](5)BF4 (45%) and [Cp3Cr3(mu(2)-OH)(mu(3)-O)(mu(2)-eta(2)-SCN4Ph)(2)](9)(MeOSO3) (53%), together with their respective free dimethylated thiolate ligands, [MeSCSNMe(C6H4)](4)BF4 and (Me2SCN4Ph)(8)MeOSO3. The reaction of 3 with Me3OBF4 resulted in the isolation of a binuclear complex, [Cp2Cr2(mu-OH)(mu-eta(2)-SCN4Ph)(2)](7)BF4 (43%), and (8)BF4 (27%). The reaction of the thiopyricline complex, CpCr(CO)(2)(SPy) (4), with I-2 also produced a similar mu(3)-oxo complex 10 (31 %), together with CpCrI2(THF) (11) and the disulfide (SPy)(2). Similar reactions with 2 and 3 and I-2 yielded species 5 and 7, together with 11 and disulfides derived from their respective ligands. Cyclic voltammograms recorded in solutions of 5 and 9 indicated that the compounds could be reduced and oxidized at very similar potentials. An EPR spectrum characteristic of a compound with axial symmetry was obtained for 9 at 7 K. Single-crystal X-ray diffraction analyses confirmed that species 7 is dinuclear, whereas 5 and 9 are structural trinuclear analogues, each containing a mu(3)-oxo central core.