Reaction of the labile cluster [Os3(CO)10(NCMe)2] with 2,2′-benzothiazyl disulfide leads to the isolation of four products, namely the known hydride complex [Os3(CO)10(µ-H)(µ- S2NC7H4)], [Os3(CO)10(µ-S2NC7H4)2] (1) in which both thiolate ligands act as three-electron donor ligands and span a single osmium-osmium vector and two isomers of [Os3(CO)9(µ-S2NC7H4)(µ3-η2-S2NC7H4)] (2, 3) in which one thiolate caps a face of the triosmium cluster via secondary nitrogen coordination. In a separate experiment thermolysis of 1 in n-heptane affords only 2. Cluster 1 contains two 2-mercaptobenzothiazolate ligands in a µ-η1 mode of bonding, while 2 and 3 are isomers differing in the relative disposition of the two 2-mercaptobenzothiazolate ligands.