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In this work, we report the synthesis, characterization and potentiometric studies of new Reor) complexes of general formula [Re02(amine)d + (amine = 1 ,2-diaminopropane, 1 ,Cdiaminobutane, N,N-diethylethylenediamine, diethylenetriamine, triethylenetetramine and N-tris(2-aminoethy1)amine). Compounds were prepared starting from [ReOzICpPhs)d and characterized by several techniques. The presence of different substituent groups in the diamines (including alkyl and amine groups) allows the presence of pendant arms. When these groups are free amino groups, they can react with acids such as H+ and M2+ cations and studied by potentiometry. The formation of very stable binuclear species was demonstrated.