Nine different Mn(beta-diketonato)(3) complexes, with beta-diketonato = dipivaloylmethanato, acetylacetonato, benzoylacetonato, dibenzoylmethanato, trifluoroacetylacetonato, trifluorothenoylacetonato, trifluorofuroylacetonato, trifluorobenzoylacetonato and hexafluoroacetylacetonato, were synthesized. The effect of the various substituents on the beta-diketonato backbone of these complexes, on the ease of oxidation and reduction of the central metal in the nine different Mn(beta-diketonato)(3) complexes, was studied by means of electrochemistry. It was found that, when adding aromatic substituents to the backbone of the beta-diketonato ligands of the complexes, the reduced/oxidized species were stabilized. It was also found that, when adding more electron withdrawing groups to the backbone of the beta-diketonato ligands of the complexes, that Mn(beta-diketonato)(3) complex was more easily reduced at a higher potential. Good linear relationships and trends were obtained between the mean value of peak oxidation and reduction potential of the Mn-III/Mn-II redox couple, and various electronic parameters and DFT calculated energies. (C) 2015 Elsevier Ltd. All rights reserved.