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Abstract: New tetraruthenated manganese (III) porphyrins were synthesized and characterized (31P NMR, cyclic voltammetry, UV–Vis). This new system presents four units of cationic “[RuCl(dppb)(X-bipy)]+”. The electrochemical and catalytic properties of the central manganese (III) show dependence on the characteristics of the peripheral ruthenium complexes as evidenced by the Mn(III)/Mn(II) reduction potential. The catalytic oxidation reactions of olefins, cyclohexene and cyclohexane, were carried out in the presence of tetrapyridyl manganese (III) porphyrins containing cationic ruthenium complex and using iodosylbenzene as oxygen donor. The performance of these new tetraruthenated porphyrins systems were evaluated and compared with the manganese porphyrin. [Copyright &y& Elsevier]