Processes such as S–C and C–H bond activations as well as C–C coupling reactions have taken place in the synthesis of the new compound [Os
3(CO)
9(μ
3-η
2,η
3,η
3-{C
5H
5FeC
5H
3CCC(S)C(Fc)CHO}] (Fc = C
5H
4FeC
5H
5), which contains an aldehyde oxametallacycle. A reactivity study of it has been carried out. In addition, other new triosmium clusters such as [Os
3(CO)
9(μ
3,η
2-C
CFc)(μ,η
1-SC
CFc)], [Os
3(CO)
10(μ,η
2-C
CFc)(μ,η
1-SC
CFc)] and [Os
3(CO)
9(μ-CO)(μ
3,η
2-FcCCSC
CFc)] have been prepared from the reaction of [Os
3(CO)
10(NCMe)
2] and FcC
CSC
CFc. All the compounds have been characterized by analytical and spectroscopic techniques. The crystal structures of [Os
3(CO)
9(μ
3,η
2-C
CFc)(μ,η
1-SC
CFc)] and [Os
3(CO)
9(μ
3-η
2,η
3,η
3-{C
5H
5FeC
5H
3CCC(S)C(Fc)CHO}] have been determined by X-ray crystallography and some electrochemical studies have also carried out.