The reaction of [Cp∗IrCl2]2 (Cp* = η5 − C5Me5) with the tridentate 3-thiapentane-1,5-dithiolate ligand, S(CH2CH2S−)2 (tpdt), led to the formation of [Cp∗Ir(η3 − tpdt)] (1) in 81% isolated yield. Subsequent reactions of 1 with [Cp∗IrCl2]2 in 2:1 and 1:1 molar equiv ratios resulted in the formation of [Cp∗Ir(μ − η2:η3 − tpdt)Cp∗IrCl][PF6] (2) and [Cp∗Irμ − η2:η3 − tpdt)Cp∗IrCl][Cp∗IrCl3] (3) in 86 and 79% yields, respectively, based on 1, whereas the reactions of 1 with [(COD)IrCl]2 (COD = 1,5-cyclooctadiene) in 2:1 and 1:1 molar equiv ratios resulted in the formation of the homo-bimetallic derivatives Cp∗Ir(μ − η1:η3 − tpdt)(COD)IrCl (4) (92% yield) and [Cp∗Ir(μ − η2:η3 − tpdt)(COD)Ir] [(COD)IrCl2] (5) (82% yield). Reactions between 1 and [(COD)RhCl]2, yielded the hetero-bimetallic derivatives Cp∗Ir(μ − η1:η3 − tpdt)(COD)RhCl (6) and [Cp∗Ir(μ − η2:η3 − tpdt)(COD)Rh][(COD)RhCl2] (7), in 92 and 93% yields, respectively. The reaction of 1 with methyl iodide gave mono-methylated derivative [Cp∗Ir(η3-C4H8S3Me)]I (8) (93% yield). All these compounds have been comprehensively characterized.