The reaction of Cp*Co(CO)2 with thionylchloride in hexane affords the doubly bridged dimer (Cp*CoCl2)2. Whereas the same reaction in more polar solvents such as CH2Cl2 or thf gives the triply bridged dinuclear cations in the salt [(Cp*Co)2(μ-Cl)3]2 [Co2Cl6], no influence of the solvent is observed in the reaction of Cp*Co(CO)2 with thionylbromide, which results in the formation of the neutral dimer (Cp*CoBr2)2. The X-ray structure analysis of (Cp*CoBr2)2 shows two edge-sharing octahedra, while that of [(Cp*Co)2(μ-Cl)3]2[Co2Cl6] shows two facesharing octahedra in the cation and two edge-sharing tetrahedra in the anion.