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• W2008559188 abstract "Abstract The cyclic voltammetry and spectroelectrochemistry of iron complexes of porphinone, porphindiones and hydroporphyrins with alkyl substituents were carried out. Except for the alkyl isobacteriochlorin complexes, the half-wave potentials of the first (FeIIIP/FeIIP), second (FeIIP/FeP−) and third (FeP−/FeP2−) waves were independent of the macrocycle identity. Any small differences were generally consistent with known substituents effects on the redox potentials. The half-wave potential of the second and third waves of iron isobacteriochlorin, Fe(2,4-DMOEiBC), (2,4-DMOEiBC=2,4-dimethyloctaethylisobacteriochlorin), though, occurred at potentials significantly more negative than the porphyrin analogue. The second wave of Fe(2,4-DMOEiBC) occurred at −1.62 V versus SCE compared to −1.26 V for Fe(OEP). Similarly, the half-wave potential for the third wave was −2.15 V versus −1.83 V for Fe(OEP). This work is in contrast with previous work on iron tetraphenylporphyrin (FeTPP) and iron tetraphenylisobacteriochlorin (FeTPiBC), where the FeP/FeP− half-wave potential was independent of macrocycle identity. The voltammetry of Fe(2,4-DMOEiBC)(Cl) in the presence of substituted pyridines was also examined. The macrocycle identity had no measurable effect in the formation constants of FeII(P) with pyridines, β2II, while there was a systematic increase in β2III (FeIII(P)(Cl) with pyridines) with increasing saturation of the macrocycle. This indicates that the Lewis acidity of the ferric complex increased with macrocycle saturation. The spectroelectrochemical reduction of iron complexes with porphyrin, chlorin, isobacteriochlorin, porphinone and porphindione was also carried out. The formation of Fe(P)− from FeII(P), where P=MOEC (methyloctaethylchlorin), led to a decrease in the molar absorptivity of the Soret band, as was observed for Fe(OEP)−, as well as an increase in the number of bands (355, 411 and 456 nm). Three Soret bands were also observed for Fe(OEPone)−, but these bands appeared as shoulders in Fe(2,4-OEPdione)− (OEPone=octaethylporphinone; OEPdione=octaethylporphindione). By contrast, the spectrum for Fe(2,4-DMOEiBC)− was quite different from Fe(OEP)−, and was much more similar to the analogous complex, Fe(TPiBC)− (TPiBC = tetraphenylisobacteriochlorin). The Soret band absorbance decreased only a small amount and no new bands in the Soret region were observed. The visible spectra of Fe(2,4-DMOEiBC) and Fe(2,4-DMOEiBC)− were quite similar to isobacteriochlorin complexes with nickel and copper. In those complexes, the changes in the visible spectra upon reduction were explained on the basis of dπ to eg*-like backbonding. The oxidation of Fe(2,4-DMOEiBC)(Cl) caused a small decrease in the absorbance of the Soret band and a bleaching of the long wavelength band. The spectrum of Fe(2,4-DMOEiBC)(Cl)+ had the same features as the previously reported superoxidized E. coli sulfite reductase." @default.
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• W2008559188 date "1994-10-01" @default.
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• W2008559188 title "Electrochemistry of nitrite reductase model compounds 5. Electrochemistry and spectroelectrochemistry of iron porphinone, porphindione and isobacteriochlorin complexes" @default.
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• W2008559188 doi "https://doi.org/10.1016/0020-1693(94)04029-x" @default.
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