Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
184486 | Electrochimica Acta | 2015 | 9 Pages |
•Cyclic voltammetry of Mn(RCOCHCOR′)3 series.•Aromatic rings (R or R′) in Mn(RCOCHCOR′)3 stabilize the reduced/oxidized species.•Mean of peak oxidation- and reduction potential relates to electronic parameters.•Mean of peak oxidation- and reduction potential relates to DFT calculated energies.
Nine different Mn(β-diketonato)3 complexes, with β-diketonato = dipivaloylmethanato, acetylacetonato, benzoylacetonato, dibenzoylmethanato, trifluoroacetylacetonato, trifluorothenoylacetonato, trifluorofuroylacetonato, trifluorobenzoylacetonato and hexafluoroacetylacetonato, were synthesized. The effect of the various substituents on the β-diketonato backbone of these complexes, on the ease of oxidation and reduction of the central metal in the nine different Mn(β-diketonato)3 complexes, was studied by means of electrochemistry. It was found that, when adding aromatic substituents to the backbone of the β-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 β-diketonato ligands of the complexes, that Mn(β-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 MnIII/MnII redox couple, and various electronic parameters and DFT calculated energies.
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