The reaction of [Cr(aet)(3)] (aet = 2-aminoethanethiolate) with Ag-I in water gave ail S-brided (Cr2Ag3I)-Ag-III pentanuclear complex [Ag-3{Cr(aet)(3)}(2)](3+) ([1](3+)). The crystal structure of [1](NO3)(3).2H(2)O was determined by X-ray analysis, which established that two fac(S)-[Cr(aet)(3)] units are linked by three Ag-I ions through S atoms (average Cr-S = 2.387(5), Ag-S = 2.403(5) Angstrom). The three Ag-I ions in [1](3+) were replaced by Au-I ions to form the corresponding (Cr2Au3I)-Au-III pentanuclear complex [Au-3{Cr(aet)(3)}(2)](3+) ([2](3+)). Treatment of [Cr(D-pen-N,O,S)(2)](-) (D-pen = D-penicillaminate) with Ag-I in water produced an S-bridged (Cr3Ag3I)-Ag-III hexanuclear complex [Ag-3{Cr(D-pen-N,O,S)(2)}(3)] ([3]), which has a cyclic structure composed of three trans(O)-[Cr(D-pen-N.O,S)(2)](-) units. Variable-temperature magnetic susceptibility data indicated the weak antiferromagnetic interaction for [1](3+) (J = -0.84 cm(-1)) while the very weak ferromagnetic interaction for [3] (J= 0.05 cm(-1)).